Heat exchange configurations for oligomerization of olefins

ABSTRACT

Disclosed herein are processes and reaction systems for controlling a temperature of an oligomerization reaction zone using a heat exchange system.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a non-provisional of and claims priority toU.S. Provisional Patent Application No. 63/224,665 filed Jul. 22, 2021and entitled “Heat Exchange Configurations for Oligomerization ofOlefins,” which application is incorporated by reference herein in itsentirety.

TECHNICAL FIELD

The present disclosure generally relates to heat exchange configurationsfor the oligomerization of olefins.

BACKGROUND

Reaction systems are used in a variety of industrial chemical processes,for example oligomerization and/or polymerization of olefins (commonlyknown as alkenes) to produce oligomers and/or polymers, respectively.For example, aluminum, nickel, zirconium, and iron based catalystsystems for the synthesis of C₄ to C₃₀₊ alpha olefins from ethylene andchromium based catalyst systems for the selective synthesis of 1-hexeneand/or 1-octene from ethylene constitute commercially significantprocesses for the preparation of alpha olefins. Ethylene oligomerizationprocesses are extremely exothermic reactions and generate a significantamount of heat which must be removed from the oligomerization reactionmixture in order to maintain a stable reaction temperature. Failure tomaintain a stable reaction temperature can lead to decreased catalystsystem stability, decreased reaction system productivity, increasedpolymer formation, decreased reactor productity, and decreased reactoronline-time, among other undesirable effects. Heat exchange systemdesign and control are important in controlling the ethyleneoligomerization temperature by removing the heat generated during theethylene oligomerization process and thus maintaining a stable reactiontemperature. Demand for alpha olefins continues to rise, and alphaolefin producers seek adequate capacity to meet demand, for example newalpha olefin production processes and improved reaction systems andprocesses of making and using same.

SUMMARY

Disclosed herein is a process comprising: a) introducing at least 1)ethylene, 2) a catalyst system or catalyst system components comprisingi) a heteroatomic ligand transition metal compound complex and anorganoaluminum compound or ii) a heteroatomic ligand, a transition metalcompound, and an organoaluminum compound, 3) optionally, an organicreaction medium, and 4) optionally, hydrogen into a reaction mixturewithin a reaction zone; b) forming an oligomer product in the reactionzone; and c) controlling a reaction mixture temperature within thereaction zone with a heat exchange system comprising a first heatexchanger providing indirect contact between at least a portion of thereaction mixture and a first heat exchange medium, the first heatexchanger comprising a first heat exchange surface having i) a firstheat exchange surface first side in contact with the at least a portionof the reaction mixture, and ii) a first heat exchange surface secondside in contact with the first heat exchange medium. In the process, apressure on the first heat exchange surface second side is less than 1atmosphere (101.3 kPa), and the first heat exchange medium has a boilingpoint at 1 atmosphere (101.3 kPa) greater than an average reactionmixture temperature on the first heat exchange surface first side and aboiling point at the pressure on the first heat exchange surface secondside less than the average reaction mixture temperature on the firstheat exchange surface first side. Also, in the process, a temperaturedifference between the average reaction mixture temperature on the firstheat exchange surface first side and a first heat exchange mediumtemperature on the first heat exchange surface second side is less than20° C.

Disclosed herein is another process comprising: a) introducing atleast 1) ethylene, 2) a catalyst system or catalyst system componentscomprising i) a heteroatomic ligand transition metal compound complexand an organoaluminum compound or ii) a heteroatomic ligand, atransition metal compound, and an organoaluminum compound, 3)optionally, an organic reaction medium, and 4) optionally, hydrogen intoa reaction mixture within a reaction zone; b) forming an oligomerproduct in the reaction zone; and c) controlling a pressure in a heatexchange system to provide a reaction mixture temperature within thereaction zone, the heat exchange system comprising a first heatexchanger providing indirect contact between at least a portion of thereaction mixture and a first heat exchange medium, the first heatexchanger comprising a first heat exchange surface having i) a firstheat exchange surface first side in contact with the at least a portionof the reaction mixture, and ii) a first heat exchange surface secondside in contact with the first heat exchange medium. In the process, apressure on the first heat exchange surface second side is less than 1atmosphere (101.3 kPa); and the first heat exchange medium has a boilingpoint at 1 atmosphere (101.3 kPa) greater than an average reactionmixture temperature on the first heat exchange surface first side and aboiling point at the pressure on the first heat exchange surface secondside less than the average reaction mixture temperature on the firstheat exchange surface first side. Also, in the process, a temperaturedifference between the average reaction mixture temperature on the firstheat exchange surface first side and a first heat exchange mediumtemperature on the first heat exchange surface second side is less than20° C.

Disclosed herein is a reaction system comprising: a) a reaction zonecontaining a reaction mixture; and b) a heat exchange system comprisinga first heat exchanger configured to provide indirect contact between atleast a portion of the reaction mixture and a first heat exchangemedium, the first heat exchanger comprising a first heat exchangesurface having i) a first heat exchange surface first side configured tocontact the reaction mixture, and ii) a first heat exchange surfacesecond side configured to contact the first heat exchange medium. In thereaction system, a pressure on the first heat exchange surface secondside of the first heat exchanger is less than 1 atmosphere (101.3 kPa),and the first heat exchange medium has a boiling point at 1 atmosphere(101.3 kPa) greater than an average reaction mixture temperature on thefirst heat exchange surface first side and a boiling point at thepressure on the first heat exchange surface second side less than theaverage reaction mixture temperature on the first heat exchange surfacefirst side. In the reaction system, a temperature difference between theaverage reaction mixture temperature on the first heat exchange surfacefirst side and a first heat exchange medium temperature of the firstheat exchange medium on the first heat exchange surface second side isless than 20° C.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures form part of the present specification and areincluded to further demonstrate certain aspects of the presentinvention. The invention may be better understood by reference to one ormore of these figures in combination with the detailed description ofspecific embodiments presented herein.

FIG. 1 illustrates a process and reaction system for controlling atemperature of a reaction mixture within an oligomerization reactionzone.

FIG. 2 illustrates another process and reaction system for controlling atemperature of a reaction mixture within an oligomerization reactionzone.

FIG. 3 illustrates another process and reaction system for controlling atemperature of a reaction mixture within an oligomerization reactionzone.

FIG. 4 illustrates an eductor and valve as pressure control devices.

FIG. 5 illustrates a valve as a pressure control device.

FIG. 6 illustrates a reaction zone for a process and/or reaction systemof FIG. 1 , FIG. 2 , and/or FIG. 3 .

While the inventions disclosed herein are susceptible to variousmodifications and alternative forms, only a few specific embodimentshave been shown by way of example in the drawings and are described indetail below. The figures and detailed descriptions of these specificembodiments are not intended to limit the breadth or scope of theinventive concepts or the appended claims in any manner. Rather, thefigures and detailed written descriptions are provided to illustrate theinventive concepts to a person of ordinary skill in the art and toenable such person to make and use the inventive concepts.

DETAILED DESCRIPTION

Illustrative embodiments of the subject matter claimed below will now bedisclosed. In the interest of clarity, not all features of an actualimplementation are described in this specification. It can beappreciated that in the development of any such actual embodiment,numerous implementation-specific decisions must be made to achieve thedevelopers' specific goals, such as compliance with system-related andbusiness-related constraints, which can vary from one implementation toanother. Moreover, it can be appreciated that such a development effort,even if complex and time-consuming, would be a routine undertaking forthose of ordinary skill in the art having the benefit of thisdisclosure.

In the description herein, various ranges and/or numerical limitationscan be expressly stated below. It should be recognized that unlessstated otherwise, it is intended that endpoints are to beinterchangeable. Further, any ranges include iterative ranges of likemagnitude falling within the expressly stated ranges or limitations. Insome instances, the description can use minimum values (or at least, orgreater than or equal to values) and maximum values (or less than orequal to values) to describe numerical limitations. These minimum valuesand maximum values can be used, without limitation and in anycombination to describe a range for described feature.

Furthermore, various modifications can be made within the scope of theinvention as herein intended, and embodiments of the invention caninclude combinations of features other than those expressly claimed. Inparticular, flow arrangements other than those expressly describedherein are within the scope of the invention.

Unless otherwise specified, the terms “contact” and “combine,” and theirderivatives, can refer to any addition sequence, order, or concentrationfor contacting or combining two or more components of the disclosedembodiments. Combining or contacting of oligomerization components canoccur in one or more reaction zones under suitable contact conditionssuch as temperature, pressure, contact time, flow rates, etc.

Within this specification, the word “reactor” refers to a single pieceof equipment such as, for example, a vessel, in which a reaction takesplace, but excludes any associated equipment such as piping, pumps, andthe like which is external to the vessel. Examples of reactors includestirred tank reactors (e.g., a continuous stirred tank reactor), plugflow reactors, or any other type of reactor.

Within this specification, term “reaction zone” refers to the portion ofa reaction system where all the necessary reaction components andreaction conditions are present such that the reaction can occur at adesired rate. That is to say that the reaction zone begins where thenecessary reaction components and reaction conditions are present tomaintain the reaction within 25 percent of the average reaction rate andthe reaction system ends where the conditions do not maintain a reactionrate within 25 percent of the average reaction rate (based upon a volumeaverage of the reaction rate of the reaction zone). For example, interms of an ethylene oligomerization process, the reaction zone beginsat the point where sufficient ethylene and active catalyst system ispresent under the sufficient reaction conditions (e.g., temperatureand/or pressure, among others) to maintain oligomer product productionat the desired rate and the reaction zone ends at a point where eitherthe catalyst system is deactivated, sufficient ethylene is not presentto sustain oligomer product production, or other reaction conditions(e.g., temperature and/or pressure, among others) are not sufficient tomaintain the oligomer product production or the desired oligomer productproduction rate. Within this specification the “reaction zone” cancomprise one or more reactors. The term “reaction zone” can be qualifiedto refer to more specific “reaction zones” by use of additionalqualifying terms. For example, the use of the term “oligomerizationreaction zone” indicates that the desired reaction within the “reactionzone” is an oligomerization.

The term “reaction system” refers to all of the equipment to produce aproduct. The term “reaction system” includes reactors, reaction zones,and all the associated equipment, associated process lines, and controlequipment which can bring the necessary component(s) into and out of thereaction system and control the reaction with the reactor(s)/reactionzone(s) of the reaction system. Within this specification the “reactionsystem” can comprise one or more reactor zones, one or more reactors,and associated equipment to produce a product. The term “reactionsystem” can be qualified to refer to more specific “reaction systems” byuse of additional qualifying terms. For example, the use of the term“oligomerization reaction system” indicates that the “reaction system”relates to an oligomerization.

Unless otherwise indicated, the definitions are applicable to thisdisclosure. If a term is used in this disclosure but is not specificallydefined herein, the definition from the IUPAC Compendium of ChemicalTerminology, 2^(nd) Ed (1997), can be applied, as long as thatdefinition does not conflict with any other disclosure or definitionapplied herein, or render indefinite or non-enabled any claim to whichthat definition can be applied. To the extent that any definition orusage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that can arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to hexeneincludes 1-hexene, 2-hexene, 3-hexene, and any other hydrocarbon having6 carbon atoms (linear, branched or cyclic) and a single carbon carbondouble bond. Additionally, the reference to a general structure or nameencompasses all enantiomers, diastereomers, and other optical isomerswhether in enantiomeric or racemic forms, as well as mixtures ofstereoisomers, as the context permits or requires. For any particularformula or name that is presented, any general formula or name presentedalso encompasses all conformational isomers, regioisomers, andstereoisomers that can arise from a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner. By way of example, an “alkyl group” formally can be derivedby removing one hydrogen atom from an alkane, while an “alkylene group”formally can be derived by removing two hydrogen atoms from an alkane.Moreover, a more general term can be used to encompass a variety ofgroups that formally are derived by removing any number (“one or more”)hydrogen atoms from a parent compound, which in this example can bedescribed as an “alkane group,” and which encompasses an “alkyl group,”an “alkylene group,” and materials have three or more hydrogens atoms,as necessary for the situation, removed from the alkane. Throughout, thedisclosure of a substituent, ligand, or other chemical moiety canconstitute a particular “group” implies that the well-known rules ofchemical structure and bonding are followed when that group is employedas described. When describing a group as being “derived by,” “derivedfrom,” “formed by,” or “formed from,” such terms are used in a formalsense and are not intended to reflect any specific synthetic methods orprocedure, unless specified otherwise or the context requires otherwise.

The term “organyl group” is used herein in accordance with thedefinition specified by IUPAC: an organic substituent group, regardlessof functional type, having one free valence at a carbon atom. Similarly,an “organylene group” refers to an organic group, regardless offunctional type, derived by removing two hydrogen atoms from an organiccompound, either two hydrogen atoms from one carbon atom or one hydrogenatom from each of two different carbon atoms. An “organic group” refersto a generalized group formed by removing one or more hydrogen atomsfrom carbon atoms of an organic compound. Thus, an “organyl group,” an“organylene group,” and an “organic group” can contain organicfunctional group(s) and/or atom(s) other than carbon and hydrogen, thatis, an organic group can comprise functional groups and/or atoms inaddition to carbon and hydrogen. For instance, non-limiting examples ofatoms other than carbon and hydrogen include halogens, oxygen, nitrogen,phosphorus, and the like. Non-limiting examples of functional groupsinclude ethers, aldehydes, ketones, esters, sulfides, amines,phosphines, and so forth. An “organyl group.” “organylene group,” or“organic group” can be aliphatic, inclusive of being cyclic or acyclic,or can be aromatic. “Organyl groups,” “organylene groups,” and “organicgroups” also encompass heteroatom-containing rings,heteroatom-containing ring systems, heteroaromatic rings, andheteroaromatic ring systems. “Organyl groups,” “organylene groups,” and“organic groups” can be linear or branched unless otherwise specified.Finally, it is noted that the “organyl group,” “organylene group,” or“organic group” definitions include “hydrocarbyl group,” “hydrocarbylenegroup,” “hydrocarbon group,” respectively, and “alkyl group,” “alkylenegroup,” and “alkane group,” respectively, as members.

For the purposes of this application, the term or variations of the term“organyl group consisting of inert functional groups” refers to anorganyl group wherein the organic functional group(s) and/or atom(s)other than carbon and hydrogen present in the functional group arerestricted to those functional group(s) and/or atom(s) other than carbonand hydrogen which do not complex with a metal compound and/or are inertunder the process conditions defined herein. Thus, the term or variationof the term “organyl group consisting of inert functional groups”further defines the particular organyl groups that can be present withinthe organyl group consisting of inert functional groups. Additionally,the term “organyl group consisting of inert functional groups” can referto the presence of one or more inert functional groups within theorganyl group. The term or variation of the term “organyl groupconsisting of inert functional groups” definition includes thehydrocarbyl group as a member (among other groups). Similarly, an“organylene group consisting of inert functional groups” refers to anorganic group formed by removing two hydrogen atoms from one or twocarbon atoms of an organic compound consisting of inert functionalgroups and an “organic group consisting of inert functional groups”refers to a generalized organic group consisting of inert functionalgroups formed by removing one or more hydrogen atoms from one or morecarbon atoms of an organic compound consisting of inert functionalgroups.

For purposes of this application, an “inert functional group” is a groupwhich does not substantially interfere with the process described hereinin which the material having an inert functional group takes part and/ordoes not complex with the metal compound of the metal complex. The term“does not complex with the metal compound” can include groups that couldcomplex with a metal compound but in particular molecules describedherein may not complex with a metal compound due to its positionalrelationship within a ligand. For example, while an ether group cancomplex with a metal compound, an ether group located at a para positionof a substituted phenyl phosphinyl group can be an inert functionalgroup because a single metal compound cannot complex with both the paraether group and the N²-phosphinyl formamidine group of the same metalcomplex molecule. Thus, the inertness of a particular functional groupis not only related to the functional group's inherent inability tocomplex the metal compound but can also be related to the functionalgroup's position within the metal complex. Non-limiting examples ofinert functional groups which do not substantially interfere withprocesses described herein can include halo (fluoro, chloro, bromo, andiodo), nitro, hydrocarboxy groups (e.g., alkoxy, and/or aroxy, amongothers), and/or sulfidyl groups, among others.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g. halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” isused herein in accordance with the definition specified by IUPAC: aunivalent group formed by removing a hydrogen atom from a hydrocarbon.Similarly, a “hydrocarbylene group” refers to a group formed by removingtwo hydrogen atoms from a hydrocarbon, either two hydrogen atoms fromone carbon atom or one hydrogen atom from each of two different carbonatoms. Therefore, in accordance with the terminology used herein, a“hydrocarbon group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group) from ahydrocarbon. A “hydrocarbyl group” “hydrocarbylene group,” and“hydrocarbon group” can be acyclic or cyclic groups, and/or can belinear or branched. A “hydrocarbyl group,” “hydrocarbylene group,” and“hydrocarbon group” can include rings, ring systems, aromatic rings, andaromatic ring systems, which contain only carbon and hydrogen.“Hydrocarbyl groups,” “hydrocarbylene groups,” and “hydrocarbon groups”include, by way of example, aryl, arylene, arene, alkyl, alkylene,alkane, cycloalkyl, cycloalkylene, cycloalkane, aralkyl, aralkylene, andaralkane groups, among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or can be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl groups are derived by removal of a hydrogen atom from a primary,secondary, or tertiary carbon atom, respectively, of an alkane. Then-alkyl group can be derived by removal of a hydrogen atom from aterminal carbon atom of a linear alkane.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturatedcarbon compound, excluding aromatic compounds. Thus, an aliphaticcompound is an acyclic or cyclic, saturated or unsaturated carboncompound, excluding aromatic compounds; that is, an aliphatic compoundis a non-aromatic organic compound. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from the carbon atom of an aliphaticcompound. Aliphatic compounds and therefore aliphatic groups can containorganic functional group(s) and/or atom(s) other than carbon andhydrogen.

The term “substituted” when used to describe a compound or group, forexample, when referring to a substituted analog of a particular compoundor group, is intended to describe any non-hydrogen moiety that formallyreplaces a hydrogen in that group, and is intended to be non-limiting. Agroup or groups can also be referred to herein as “unsubstituted” or byequivalent terms such as “non-substituted,” which refers to the originalgroup in which a non-hydrogen moiety does not replace a hydrogen withinthat group. “Substituted” is intended to be non-limiting and includeinorganic substituents or organic substituents.

The term “reaction zone effluent,” and it derivatives (e.g.,oligomerization reaction zone effluent, trimerization reaction zoneeffluent, tetramerization reaction zone effluent, or trimerization andtetramerization reaction zone effluent) generally refers to all thematerial which exits the reaction zone through a reaction zoneoutlet/discharge which discharges a reaction mixture and can includereaction zone feed(s) (e.g., olefin, catalyst system or catalyst systemcomponents, and/or solvent), and/or reaction product (e.g., oligomerproduct including oligomers and non-oligomers, trimerization productincluding trimer and non-trimer, tetramerization product includingtetramer and non-tetramer, or trimerization and tetramerization productincluding trimer and tetramer and non-trimer and tetramer). The term“reaction zone effluent” and its derivatives can be qualified to referto certain portions by use of additional qualifying terms. For example,while reaction zone effluent refers to all material which exits thereaction zone through the reaction zone outlet/discharge, a reactionzone oligomer product effluent refers to only the oligomer productwithin the reaction zone effluent.

As utilized in the present application and claims, the word “control”and its derivatives (e.g., “controlling” and “controlled”, among anyothers) is intended to apply to situation where the particular parameteris actively maintained, adjusted, increased, and/or decreased unlessspecifically indicated otherwise. For example, a reference tocontrolling a reaction mixture temperature includes situations where thereaction temperature is actively maintained, adjusted, increased, and/ordecreased.

Disclosed herein are processes and reaction systems for controlling atemperature of an oligomerization reaction zone. Oligomerizationreactions are exothermic in nature, and thus produce heat that must beremoved from the reaction zone in order to control the temperature ofthe reaction zone.

In an aspect, the present application relates to a process comprisingproviding or controlling a reaction mixture temperature (or averagereaction mixture temperature) within a reaction zone with a heatexchange system, the heat exchange system comprising a first heatexchanger providing indirect contact between at least a portion of thereaction mixture and a first heat exchange medium, the first heatexchanger comprising a first heat exchange surface having i) a firstheat exchange surface first side in contact with at least a portion ofthe reaction mixture and ii) a first heat exchange surface second sidein contact with the first heat exchange medium; where a pressure on thefirst heat exchange surface second side (or on the first heat exchangemedium) can be, or can be controlled to be, less than 1 atmosphere(101.3 kPa). The process comprising controlling (or providing) areaction mixture temperature within the reaction zone can furthercomprise providing or controlling the pressure on the first heatexchange surface second side (or first heat exchange medium) to controlthe reaction mixture temperature (or average reaction mixturetemperature) within the reaction zone. In another aspect, the presentapplication relates to a comprising providing or controlling a pressurein a heat exchange system to provide a reaction mixture temperature (oraverage reaction mixture temperature) within a reaction zone, the heatexchange system comprising a first heat exchanger providing indirectcontact between the reaction mixture and a first heat exchange medium,the first heat exchanger comprising a first heat exchange surface havingi) a first heat exchange surface first side in contact with the reactionmixture and ii) a first heat exchange surface second side in contactwith the first heat exchange medium; where a pressure on the first heatexchange surface second side of the first heat exchanger can be or canbe controlled to be less than 1 atmosphere (101.3 kPa). The processcomprising providing or controlling a pressure in a heat exchange systemcan further comprise controlling the reaction mixture temperature (oraverage reaction mixture temperature) within a reaction zone. In yetanother aspect, the present application relates to a reaction systemcomprising: a) a reaction zone containing a reaction mixture; and b) aheat exchange system comprising a first heat exchanger configured toprovide indirect contact between the reaction mixture and a first heatexchange medium, the first heat exchanger comprising a first heatexchange surface having i) a first heat exchange surface first sideconfigured to contact the reaction mixture, and ii) a first heatexchange surface second side configured to contact a first heat exchangemedium; where a pressure on the first heat exchange surface second sidecan be or can be controlled to be less than 1 atmosphere (101.3 kPa).

The first heat exchange medium can have a boiling point at 1 atmosphere(101.3 kPa) greater than an average reaction mixture temperature on thefirst heat exchange surface first side and can have a boiling point atthe pressure on the first heat exchange surface second side less thanthe average reaction mixture temperature on the first heat exchangesurface first side. Generally, the first heat exchange medium can haveany boiling point at 1 atmosphere (101.3 kPa) which can provide adesired boiling point at the pressure on the first heat exchange surfacesecond side that is less than the average reaction mixture temperatureon the first heat exchange surface first side. Additional aspects of thefirst heat exchange medium (e.g., potential first heat exchange mediumsand physical properties such as potential boiling point, among otherthings) are independently described herein and can be utilized withoutlimitation and in any combination to further describe the first heatexchange medium utilized in the processes described herein.

When the reaction mixture temperature (or the average reaction mixturetemperature) within the reaction zone (or on the first heat exchangesurface first side) is greater than boiling point of the first heatexchange medium on the first heat exchange surface second side, bothliquid phase of the first heat exchange medium and vapor phase of thefirst heat exchange medium can be present in the heat exchange system(or in the first heat exchanger). As such, in an aspect, a first part ofat least a portion of the reaction mixture on the first heat exchangesurface first side can indirectly contact a liquid phase of the firstheat exchange medium on the first heat exchange surface second side, anda second part of the at least a portion of the reaction mixture on thefirst heat exchange surface first side can indirectly contact a vaporphase of the first heat exchange medium that are on the first heatexchange surface second side. As such, there can be a first level of aliquid phase of the first heat exchange medium on the first heatexchange surface second side. In an aspect, the first level of a liquidphase of the first heat exchange medium on the first heat exchangesurface second side can be controlled. In another aspect, controlling(maintaining, adjusting, increasing and/or decreasing) the first levelof the liquid phase of the first heat exchange medium on the first heatexchange surface second side can be utilized to control the reactionmixture temperature (or average reaction mixture temperature) on thefirst heat exchange surface first side.

The amount of the reaction mixture that can indirectly contact liquidphase of the first heat exchange medium or the first level of the liquidphase of the first heat exchange medium on the first heat exchangesurface second side can be provided as 1) a percentage of the at least aportion of the reaction mixture on the first heat exchange surface firstside which indirectly contacts the liquid phase of the first heatexchange medium on the first heat exchange surface second side; 2) apercentage of the surface area of the first heat exchange surface secondside which contacts the liquid phase of the first heat exchange medium;3) a volume ratio of the liquid phase of the first heat exchange mediumin the first heat exchanger (or on the first heat exchange surfacesecond side) to the vapor phase of the first heat exchange medium in thefirst heat exchanger (or on the first heat exchange surface secondside); or 4) any combination thereof. The percentage of the at least aportion of the reaction mixture on the first heat exchange surface firstside which indirectly contacts a liquid phase of the first heat exchangemedium on the first heat exchange surface second side can be, or can becontrolled to be greater than or equal to 50%, 60%, 70%, 75%, 80%, or90% by volume; alternatively or additionally, less than or equal to 95%,90%, 85%, 80%, 75%, or 70% by volume. In an aspect, the percentage ofthe at least a portion of the reaction mixture on the first heatexchange surface first side which indirectly contacts a liquid phase ofthe first heat exchange medium on the first heat exchange surface secondside can be or can be controlled to be in a range from any minimumpercentage disclosed herein to any maximum percentage disclosed herein.In some non-limiting aspects, the percentage of the at least a portionof the reaction mixture on the first heat exchange surface first sidewhich indirectly contacts a liquid phase of the first heat exchangemedium on the first heat exchange surface second side can be or can becontrolled to be in a range from 50% to 95%, from 60% to 95%, from 60%to 90%, from 70% to 90%, from 70% to 85%, or from 75% to 85%, by volume.Other percentages of the at least a portion of the reaction mixture onthe first heat exchange surface first side which indirectly contacts aliquid phase of the first heat exchange medium on the first heatexchange surface second side are readily apparent to those skilled inthe art with the aid of this disclosure. The percentage of the surfacearea of the first heat exchange surface second side which contacts theliquid phase of the first heat exchange medium can be or can becontrolled to be at least 50%, 60%, 70%, 75%, 80%, or 90%; alternativelyor additionally, less than or equal to 95%, 90%, 85%, 80%, 75%, or 70%.In an aspect, the percentage of the surface area of the first heatexchange surface second side which contacts the liquid phase of thefirst heat exchange medium can be or can be controlled to be in a rangefrom any minimum percentage disclosed herein to any maximum percentagedisclosed herein. In some non-limiting aspects, the percentage of thesurface area of the first heat exchange surface second side whichcontacts the liquid phase of the first heat exchange medium can be orcan be controlled to be in a range from 50% to 95%, from 60% to 95%,from 60% to 90%, from 70% to 90%, from 70% to 85%, or from 75% to 85%.Other percentages of the surface area of the first heat exchange surfacesecond side which contacts the liquid phase of the first heat exchangemedium are readily apparent to those skilled in the art with the aid ofthis disclosure. The volume ratio of the liquid phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) to the vapor phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) can be or can be controlled to be greaterthan or equal to 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1;alternatively or additionally, less than or equal to 20:1, 10:1, 6:1,4:1, 3:1, or 2.5:1. In an aspect, the volume ratio of the liquid phaseof the first heat exchange medium in the first heat exchanger (or on thefirst heat exchange surface second side) to the vapor phase of the firstheat exchange medium in the first heat exchanger (or on the first heatexchange surface second side) can be or can be controlled to be in arange from any minimum percentage disclosed herein to any maximumpercentage disclosed herein. In some non-limiting aspects, the volumeratio of the liquid phase of the first heat exchange medium in the firstheat exchanger (or on the first heat exchange surface second side) tothe vapor phase of the first heat exchange medium in the first heatexchanger (or on the first heat exchange surface second side) can be orcan be controlled to be in a range from 1:1 to 20:1, from 1.5:1 to 20:1,from 1.5:1 to 9:1, from 2:1 to 9:1, from 2.5:1 to 6:1, or from 3:1 to6.1; among other ratios disclosed herein. Other volume ratios of theliquid phase of the first heat exchange medium in the first heatexchanger (or on the first heat exchange surface second side) to thevapor phase of the first heat exchange medium in the first heatexchanger (or on the first heat exchange surface second side) arereadily apparent to those skilled in the art with the aid of thisdisclosure.

The heat exchange system of the processes and/or reaction systemsdescribed herein can further comprise a second heat exchanger providingindirect contact between the first heat exchange medium and a secondheat exchange medium, the second heat exchanger comprising a second heatexchange surface having i) a second heat exchange surface first side incontact with the first heat exchange medium, and ii) a second heatexchange surface second side in contact with the second heat exchangemedium where a pressure on the second heat exchange surface first sideof the second heat exchanger can be or can be controlled to be apressure less than 1 atmosphere (101.3 kPa). In an aspect, the secondheat exchange surface does not contact the reaction mixture. In anaspect, the heat exchange system can further comprise a plurality ofconduits connecting the first heat exchanger and the second heatexchanger and allowing for flow of the first heat exchange mediumbetween the first heat exchange surface second side and the second heatexchange surface first side. At least one of one or more conduits canallow for flow of the first heat exchange medium from the first heatexchange surface second side to the second heat exchange surface firstside and at least one of the one or more conduits can allow for flow ofthe first heat exchange medium from the second heat exchange surfacefirst side to the first heat exchange surface second side. When the heatexchange system contains a liquid phase of the first heat exchangemedium and a vapor phase of the first heat exchange medium, at least oneof one or more conduits can allow for flow of vapor phase of the firstheat exchange medium from the first heat exchange surface second side tothe second heat exchange surface first side, and at least one of the oneor more conduits can allow for flow of liquid phase of the first heatexchange medium from the second heat exchange surface first side to thefirst heat exchange surface second side.

Generally, the first and second heat exchange surfaces can have anyorientation that can provide the desired indirect contact between thereaction mixture and the first heat exchange medium or the first heatexchange medium and second heat exchange medium. The first heat exchangesurface can comprise horizontally oriented tubes or plates, orvertically oriented tubes or plates; alternatively, horizontallyoriented tubes or plates; or alternatively, vertically oriented tubes orplates. The second heat exchange surface can comprise horizontallyoriented tubes or plates, or vertically oriented tubes or plates;alternatively, horizontally oriented tubes or plates; or alternatively,vertically oriented tubes or plates. In an aspect, the first heatexchange surface can comprise horizontally oriented tubes or plates, andthe second heat exchange surface can comprise vertically oriented tubesor plates.

In aspects where the heat exchange system contains both liquid phase ofthe first heat exchange medium and vapor phase of the first heatexchange medium, liquid phase and vapor phase of the first heat exchangemedium can contact the second heat exchange surface first side (orindirectly contact the second heat exchange medium). In this aspect, afirst part of the at least a portion of the reaction mixture on thefirst heat exchange surface first side indirectly contacts a liquidphase of the first heat exchange medium on the first heat exchangesurface second side, and a second part of the at least a portion of thereaction mixture on the first heat exchange surface first sideindirectly contacts a vapor phase of the first heat exchange medium onthe first heat exchange surface second side; and at least a first partof the second heat exchange medium on the second heat exchange surfacesecond side indirectly contacts the vapor phase of the first heatexchange medium on the second heat exchange surface first side, and asecond part of the second heat exchange medium on the second heatexchange surface second side indirectly contacts liquid phase of thefirst heat exchange medium on the second heat exchange surface firstside. In this aspect, there can be a second level of liquid phase of thefirst heat exchange medium on second heat exchange surface first side.The first level of the liquid phase of the first heat exchange medium isdescribed herein and can be utilized without limitation to described thefirst level of the first heat exchange medium in aspect where the heatexchange system includes the first heat exchanger and the second heatexchanger. Generally, the second level of liquid phase of the first heatexchange medium can be any level provided herein. The second level ofliquid phase of the first heat exchange medium can be provided as 1) apercentage of the second heat exchange medium on the second heatexchange surface second side which indirectly contacts the liquid phaseof the first heat exchange medium on the second heat exchange surfacefirst side; 2) a volume ratio of liquid phase of the first heat exchangemedium in the second heat exchanger (or on the second heat exchangesurface first side) to vapor phase of the first heat exchange medium inthe second heat exchanger (or on the second heat exchanger surface firstside); or 3) any combination thereof. The percentage of the second heatexchange medium on the second heat exchange surface second side whichindirectly contacts the liquid phase of the first heat exchange mediumon the second heat exchange surface first side can be or can becontrolled to be least 50%, 60%, 70%, 80%, or 90%, by volume;alternatively or additionally, less than or equal to 95%, 90%, 85%, 80%,75%, or 70%, by volume. In an aspect, the second heat exchange medium onthe second heat exchange surface second side which indirectly contactsthe liquid phase of the first heat exchange medium on the second heatexchange surface first side can be or can be controlled to be in a rangefrom any minimum percentage disclosed herein to any maximum percentagedisclosed herein. In some non-limiting aspects, the second heat exchangemedium on the second heat exchange surface second side which indirectlycontacts the liquid phase of the first heat exchange medium on thesecond heat exchange surface first side can be or can be controlled tobe in a range from 50% to 95%, from 60% to 95%, from 60% to 90%, from70% to 90%, from 70% to 85%, or from 75% to 85%, by volume. Otherpercentages of the second heat exchange medium on the second heatexchange surface second side which indirectly contacts the liquid phaseof the first heat exchange medium on the second heat exchange surfacefirst side are readily apparent to those skilled in the art with the aidof this disclosure. The volume ratio of the liquid phase of the firstheat exchange medium in the second heat exchanger (or on the second heatexchange surface first side) to the vapor phase of the first heatexchange medium in the second heat exchanger (or on the second heatexchange surface first side) can be or can be controlled to be greaterthan or equal to 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1;alternatively or additionally, less than or equal to 20:1, 10:1, 6:1,4:1, 3:1, or 2.5:1. In an aspect, the volume ratio of the liquid phaseof the first heat exchange medium in the second heat exchanger (or onthe second heat exchange surface first side) to the vapor phase of thefirst heat exchange medium in the second heat exchanger (or on thesecond heat exchange surface first side) can be or can be controlled tobe in a range from any minimum percentage disclosed herein to anymaximum percentage disclosed herein. In some non-limiting aspects, thevolume ratio of the liquid phase of the first heat exchange medium inthe second heat exchanger (or on the second heat exchange surface firstside) to the vapor phase of the first heat exchange medium in the secondheat exchanger (or on the second heat exchange surface first side) canbe or can be controlled to be in a range from 1:1 to 20:1, from 1.5:1 to20:1, from 1.5:1 to 9:1, from 2:1 to 9:1, from 2.5:1 to 6:1, or from 3:1to 6.1. Other volume ratios of the liquid phase of the first heatexchange medium in the second heat exchanger (or on the second heatexchange surface first side) to the vapor phase of the first heatexchange medium in the second heat exchanger (or on the second heatexchange surface first side) are readily apparent to those skilled inthe art with the aid of this disclosure. In an aspect, the second levelof the liquid phase of the first heat exchange medium on the second heatexchange surface first side is vertically higher relative to a commonreference point on the ground than the first level of the liquid phaseof the first heat medium on the first heat exchange surface second side.The second heat exchange surface first side being vertically higherrelative to a common reference point on the ground than the first levelof the liquid phase of the first heat medium on the first heat exchangesurface second side enables the use of gravity to allow flow of theliquid phase of the first heat exchange medium from the second heatexchanger (or the second heat exchange surface first side) to the firstheat exchanger (or the first heat exchange surface second side).Additionally, the second heat exchange surface first side beingvertically higher relative to a common reference point on the groundthan the first level of the liquid phase of the first heat medium on thefirst heat exchange surface second side enables the use of the secondlevel of liquid phase of the first heat exchange medium as a method tocontrol the pressure on the first heat exchange surface second sideand/or the pressure on the second heat exchange surface first side(and/or the first heat exchange medium).

Generally, for any process and/or reaction system described herein, thepressure less than 1 atmosphere (101.3 kPa) on the first heat exchangesurface second side (and/or the second heat exchange surface first sideand/or the first heat exchange medium) can be any pressure whichprovides or can control a desired reaction mixture temperature (oraverage reaction mixture temperature). The pressure less than 1atmosphere (101.3 kPa) can be a minimum the pressure of 0.1, 0.12, 0.15,0.2, 0.25, 0.3, 0.375, or 0.45 atmospheres; alternatively oradditionally, a maximum pressure of 0.9, 0.875, 0.85, 0.8, 0.75, or 0.7atmospheres. The pressure less than 1 atmosphere (101.3 kPa) can rangefrom any minimum pressure described herein to any maximum pressuredescribed herein. Non-limiting examples for pressures less than 1atmosphere (101.3 kPa) include a pressure in the range of 0.1 to 0.9,0.12 to 0.9, 0.15 to 0.875, 0.2 to 0.875, 0.3 to 0.85, 0.375 to 0.85, or0.45 to 0.85 atmospheres. Other suitable ranges for the pressure lessthan 1 atmosphere (101.3 kPa) on the first heat exchange surface secondside (or second heat exchange surface first side or the first heatexchange medium) are readily apparent from the present disclosure.

The heat exchange system of the processes and/or reaction systemsdescribed herein can be utilized to provide and/or control the reactionmixture temperature (or average reaction mixture temperature) in thereaction zone (or contacting the first heat exchange surface firstside). Generally, the reaction mixture temperature (or average reactionmixture temperature) in the reaction zone (or on the first heat exchangesurface first side) can be any reaction mixture temperature (or averagereaction mixture temperature) greater than the boiling point of theboiling point of the first heat exchange medium at the pressure of lessthan 1 atmosphere (101.3 kPa) on the first heat exchange surface secondside (or second heat exchange surface first side or the first heatexchange medium). The reaction mixture temperature (or the averagereaction mixture temperature) in the reaction zone (or on the first heatexchange surface second side) can have a minimum temperature of 0° C.25° C., 40° C., 50° C., 60° C., 70° C., or 75° C.; alternatively oradditionally, a maximum temperature of 120° C. 110° C., 100° C., or 95°C. or 90° C. The reaction mixture temperature (or the average reactionmixture temperature) in the reaction zone (or on the first heat exchangesurface second side) can range from any minimum temperature disclosedherein to any maximum temperature disclosed herein. Non-limiting rangesfor the reaction mixture temperature (or the average reaction mixturetemperature) in the reaction zone (or on the first heat exchange surfacesecond side) can be in a range from 0° C. to 120° C., from 25° C. to120° C., from 40° C. to 110° C., from 50° C. to 100° C., from 50° C. to100° C., from 60° C. to 95° C. from 70° C. to 95° C., from 75° C. to 95°C., or from 75° C. to 90° C. Other suitable ranges for the reactionmixture temperature (or the average reaction mixture temperature) in thereaction zone (or on the first heat exchange surface second side) arereadily apparent from the present disclosure.

Generally, the processes and reaction systems described herein can haveany pressure less than 1 atmosphere (101.3 kPa) described herein on thefirst heat exchange surface second side (or second heat exchange surfacefirst side or first heat exchange medium). Generally, the pressure lessthan less than 1 atmosphere (101.3 kPa) can be supplied by any meanscapable of providing and/or controlling a pressure less than 1atmosphere (101.3 kPa). In an aspect, the heat exchange system of theprocesses and/or reaction systems described herein can further compriseone or more pressure control devices. In an aspect, the one or morepressure control devices can be fluidly connected to the first heatexchange surface first side; alternatively, or additionally fluidlyconnected to the second heat exchange surface first side. In anotheraspect, at least one of the one or more pressure control devices can bein fluid communication with (fluidly connected to) at least one of theplurality of conduits; alternatively, in fluid communication with(fluidly connected to) at least one of the plurality of conduitsallowing for flow of the first heat exchange medium between the firstheat exchanger and the second heat exchanger; or alternatively, in fluidcommunication with a conduit allowing for flow of the first heatexchange medium from the first heat exchange surface second side to thesecond heat exchange surface first side. Pressure control devices areindependently described herein, and these independently describedpressure control devices can be utilized without limitation to furtherdescribe the process and reaction systems described herein. In anaspect, the one or more pressure control devices can provide an initialpressure less than 1 atmosphere (101.3 kPa), as described herein, on thefirst heat exchange surface second side (and/or second heat exchangesurface first side and/or first heat exchange medium), can provide orcontrol the pressure on the first heat exchange surface second side(and/or second heat exchange surface first side and/or first heatexchange medium), can provide or control the first level of the liquidphase of the first heat exchange medium on the first heat exchangesurface second side, can remove non-condensable components from thefirst heat exchange medium, or any combination thereof; alternatively,the one or more pressure control devices can provide an initial pressureless than 1 atmosphere (101.3 kPa), as described herein, on the firstheat exchange surface second side; alternatively, can control thepressure on the first heat exchange surface second side (and/or secondheat exchange surface first side and/or first heat exchange medium), orcontrol the first level of the liquid phase of the first heat exchangemedium on the first heat exchange surface second side; alternatively,can control the pressure on the first heat exchange surface second side;alternatively, can control the first level of the liquid phase of thefirst heat exchange medium on the first heat exchange surface secondside (and/or second heat exchange surface first side and/or first heatexchange medium); or alternatively, can remove non-condensablecomponents from the first heat exchange medium. In an aspect, thepressure on the first heat exchange surface second side (and/or thesecond heat exchange surface first side, and/or the first heat exchangemedium) can be provided or controlled by a set point on at least one ofthe one or more pressure control devices.

Since the first heat exchange medium indirectly contacts the reactionmixture through the first heat exchange surface, the reaction mixturetemperature (or the average reaction mixture temperature) in thereaction zone (or on the first heat exchange surface first side) can becontrolled by controlling a parameter affecting the temperature of thefirst heat exchange medium and/or a parameter affecting the indirectcontact of the reaction mixture and the first heat exchange mediumthrough the first heat exchange surface. Non-limiting parameters whichcan affect the temperature of the first heat exchange medium or aparameter affecting the indirect contact of the reaction mixture and thefirst heat exchange medium through the first heat exchange surface(which in turn can be used to control the reaction mixture temperatureor the average reaction mixture temperature) can include the pressure onthe first heat exchange surface second side (and/or on the second heatexchange surface first side, and/or on the first heat exchange medium),the first level of the liquid phase of the first heat exchange medium onthe first heat exchange surface second side, and the second level of theliquid phase of the first heat exchange medium on the second heatexchange surface first side, among other parameters. In an aspect,controlling the reaction mixture temperature (or the average reactionmixture temperature) in the reaction zone (or on the first heat exchangesurface first side) can comprise controlling the pressure on the firstheat exchange surface second side (and/or second heat exchange surfacefirst side, and/or the first heat exchange medium), controlling thefirst level of the liquid phase of the first heat exchange medium on thefirst heat exchange surface second side, controlling the second level ofthe liquid phase of the first heat exchange medium on the second heatexchange surface first side, or any combination thereof; controlling thepressure on the first heat exchange surface second side (and/or secondheat exchange surface first side, and/or the first heat exchangemedium), controlling the first level of the liquid phase of the firstheat exchange medium on the first heat exchange surface second side, orany combination thereof; alternatively, controlling the pressure on thefirst heat exchange surface second side (or on the first heat exchangemedium or on the second heat exchange surface first side);alternatively, controlling the first level of the liquid phase of thefirst heat exchange medium on the first heat exchange surface secondside; or alternatively, controlling the second level of the liquid phaseof the first heat exchange medium on the second heat exchange surfacefirst side. In an aspect, controlling the reaction mixture temperature(or average reaction mixture temperature) can comprise controlling thepressure on the first heat exchange surface first side and on the secondheat exchange surface first side by controlling the pressure provided bythe one or more pressure control devices.

In an aspect, controlling the first level of the liquid phase of thefirst heat exchange medium (or controlling the reaction mixturetemperature or average reaction mixture temperature in the reactionzone) can comprise a) controlling a second level of a liquid phase ofthe first heat exchange medium on the second heat exchange surface firstside; b) adding first heat exchange medium to the heat exchange systemor removing a portion of the first heat exchange medium from the heatexchange system; c) controlling the pressure on the first heat exchangesurface second side (and/or first heat exchange medium, and/or secondheat exchange surface first side); or d) any combination thereof;alternatively, controlling a second level of a liquid phase of the firstheat exchange medium on the second heat exchange surface first side;adding first heat exchange medium to the heat exchange system orremoving a portion of the first heat exchange medium from the heatexchange system; or any combination thereof; alternatively, controllinga second level of a liquid phase of the first heat exchange medium onthe second heat exchange surface first side; alternatively, adding firstheat exchange medium to the heat exchange system or removing a portionof the first heat exchange medium from the heat exchange system; oralternatively, controlling the pressure on the first heat exchangesurface second side (and/or first heat exchange medium, and/or secondheat exchange surface first side). In an aspect, controlling thepressure on the first heat exchange surface second side (and/or firstheat exchange medium, and/or second heat exchange surface first side),which can be utilized to control the first level of the first heatexchange medium on the first heat exchange surface second side or tocontrol the reaction mixture temperature (or average reaction mixturetemperature) in the reaction zone can comprise controlling the pressureset point of the one or more pressure control points. In other aspects,controlling the reaction mixture temperature (or average reactionmixture temperature) can comprise increasing or decreasing the flow rateof the first heat exchange medium.

Generally, when controlling the pressure on the first heat exchangesurface second side (and/or on the second heat exchange surface firstside and/or the first heat exchange medium) to control a reactionmixture temperature (or average reaction mixture temperature) and/orcontrol a first level of liquid phase of the first heat exchange medium,the pressure can be controlled (maintained, adjusted, increased ordecreased) to be any pressure less than pressure less than 1 atmosphere(101.3 kPa) as described herein. Generally, when controlling the firstlevel of liquid phase of the first heat exchange medium on the firstheat exchange surface second side to control a reaction mixturetemperature (or average reaction mixture temperature), the first levelof liquid phase of the first heat exchange medium on the first heatexchange surface second side can be controlled to be any first level ofliquid phase of the first heat exchange medium on the first heatexchange surface second side as disclosed herein. Generally, whencontrolling the second level of liquid phase of the first heat exchangemedium on the second heat exchange surface first side to control areaction mixture temperature (or average reaction mixture temperature)and/or control a first level of liquid phase of the first heat exchangemedium, the second level of liquid phase of the first heat exchangemedium on the second heat exchange surface first side can be controlledto be any second level of liquid phase of the first heat exchange mediumon the second heat exchange surface second side as disclosed herein.

FIG. 1 illustrates a portion of a non-limiting reaction system 100,including a heat exchange system 110 and at least a portion of areaction zone 101. In an aspect, the reaction zone 101 can contain areaction mixture. In an aspect, the heat exchange system 110 can beutilized to control a reaction mixture temperature (or an averagereaction mixture temperature) within reaction zone 101, and/or apressure in the heat exchange system. The heat exchange system 110includes the heat exchanger 111 (also referred to herein as first heatexchanger or first heat exchanger 111 for clarity) and process lines 201and 202. The heat exchange system 110 is discussed in more detailherein. The at least a portion of reaction zone 101 of reaction system100 is any location in the process and reaction system 100 where all thenecessary reaction components (e.g., at least ethylene, a catalystsystem or catalyst system components, optionally an organic reactionmedium, and optionally hydrogen) and reaction conditions (e.g., processconditions as described herein) are present such that oligomerizationreaction can occur at a desired rate. The at least a portion of reactionzone 101 is discussed in more detail herein. One or more reaction zoneinlets (not shown) can be included in reaction system 100 tointroduce/feed one or more reaction mixture components (e.g., ethylene,catalyst system or catalyst system components, optionally organicreaction medium, optionally hydrogen, or combinations thereof) into thereaction mixture. The one or more reaction zone inlets can be configuredto introduce/feed the one or more reaction components into the reactionmixture. One or more reaction zone outlets (not shown) can be includedto remove reaction mixture from the reaction zone. The one or morereaction zone outlets are configured to withdraw reaction mixture fromthe reaction zone. Reaction system 100 and heat exchange system 110 canadditionally comprise any equipment associated with reaction systems,such as a vessel, one or more control devices (e.g., a PID controller),measurement instruments (e.g., thermocouples, transducers, and flowmeters), alternative inlet lines and outlet lines (all not shown).

The heat exchanger 111 is configured to provide indirect contact betweenat least a portion of the reaction mixture and a heat exchange medium(also referred to herein as the first heat exchange medium for clarity).Indirect contact refers to contact through a heat conductive materialsuch as the heat exchange surface 112 (also referred to herein as firstheat exchange surface or first heat exchange surface 111, for clarity)described herein (e.g., a first heat exchange surface which can beembodied as metal tubes or metal plates), without any direct contact ormixing between the reaction mixture and the heat exchange medium. Theheat exchanger Ill comprises heat exchange surface 112 that isconfigured to separate the reaction mixture from the heat exchangemedium inside the heat exchanger 111 and thus provide indirect contactbetween the heat exchange medium and the reaction mixture. The heatexchange surface 12 separates the heat exchanger 111 into two sections:a first section through which the reaction mixture flows and a secondsection through which the heat exchange medium flows. In aspects, theheat exchanger 111 comprises a heat exchange surface first side 113(i.e., first side 113 of the heat exchange surface 112 and also referredto herein as first heat exchange surface first side or first heatexchange surface first side 113, for clarity) configured to contact thereaction mixture and a heat exchange surface second side 114 (i.e.,second side 114 of the heat exchange surface 112 and also referred toherein as first heat exchange surface second side or first heat exchangesurface second side 114, for clarity) is configured to contact the heatexchange medium. In an aspect, the heat exchange surface 112 can behorizontally oriented, e.g., embodied as horizontally oriented tubes orplates, or vertically oriented, e.g., embodied as vertically orientedtubes or plates; alternatively, horizontally oriented; or alternatively,vertically oriented. In an aspect, the pressure in heat exchanger system110 that is controlled can be the pressure on the heat exchange surfacesecond side 114 (or on the heat exchange medium).

Heat exchange medium inflow line 201 and heat exchange medium outflowline 202 (representing a plurality of conduits) are connected to theheat exchanger 111. The heat exchange medium can flow into the heatexchanger 111 via inflow line 201 configured to allow for flow of theheat exchange medium into the heat exchanger 111, and through heatexchanger 111, where the heat exchange medium contacts the heat exchangesurface second side 114. For an exothermic reaction such asoligomerization reactions, heat is indirectly transferred from thereaction mixture to the heat exchange medium via contact of the reactionmixture with the heat exchange surface first side 113 and by contactingthe heat exchange medium with the heat exchange surface second side 114.Flow of the heat exchange medium through the heat exchanger 111 carriesheated heat exchange medium out of the heat exchanger via outflow line202 configured to allow for flow of the heat exchange medium out of theheat exchanger 111.

The direction of flow of the reaction mixture relative to the directionof flow of the heat exchange medium in the heat exchanger 111 can becounter flow, concurrent flow, cross flow, or a combination thereof. Inan aspect, the heat exchange surface 112 can include multiple passeswhere the reaction mixture indirectly contacts the heat exchange medium.In aspects, the heat exchanger 111 can be of a tubular design (e.g.,shell and tube heat exchanger), a plate design (e.g., shell and plateheat exchanger), or a combination of tubular and plate design;alternatively, tubular design; alternatively, a plate design; oralternatively, a combination of tubular and plate design. In any design,the heat exchange surface 112 can be embodied as a tube and/or plateconfigured to provide the indirect contact between the reaction mixtureand the heat exchange medium. It is contemplated that the reactionmixture can flow on the tube side or plate side of the heat exchangerIll while the heat exchange medium flows on the shell side;alternatively, the reaction mixture can flow on the shell side while theheat exchange medium can flow on the tube side or plate side. The heatexchange medium can comprise a liquid phase of the heat exchange medium,a vapor phase of the heat exchange medium, or liquid phase and vaporphase and vapor phase of the heat exchange medium; alternatively, aliquid phase of the heat exchange medium; alternatively, a vapor phaseof the heat exchange medium; or alternatively, liquid and vapor phase ofthe heat exchange medium. In some aspects, the heat exchange medium canenter heat exchanger 111 (via line 201) as a liquid phase of the heatexchange medium and exit heat exchanger 111 (via 202) as a liquid phaseof the heat exchange medium such that the reaction mixture in thereaction zone 101 that is on the heat exchange surface first side 113indirectly contacts only the liquid phase of the heat exchange medium onthe heat exchange surface second side 114. In another aspect, it iscontemplated that i) the heat exchange medium remains in liquid phaseduring indirect contact with the reaction mixture through the heatexchange surface 112 and that ii) the heat exchange medium is in thevapor phase in the space of heat exchanger 111 that is above the heatexchange surface 112 (e.g., such that the vapor phase does not contactthe heat exchange surface 112). It is also contemplated that liquid heatexchange medium within the heat exchanger 111 can vaporize throughindirect contact with the reaction mixture through heat exchange surface112. Thus, the heat exchange medium can be present on the heat exchangesurface second side 114 in both the liquid phase and the vapor phase. Inan aspect, the heat exchange medium can enter heat exchanger 111 (vialine 201) as a liquid phase of the heat exchange medium and exit heatexchanger 111 (via 202) as a vapor phase of the heat exchange medium.Thus, a first part of the at least a portion of the reaction mixture inthe heat exchanger 111 (or on the heat exchange surface first side 113)indirectly contacts a liquid phase of the heat exchange medium in theheat exchanger 11 (or on the heat exchange surface second side 114) anda second part of the at least a portion of the reaction mixture in theheat exchanger 111 (or on the heat exchange surface first side 113)indirectly contacts a vapor phase of the heat exchange medium in theheat exchanger 111 (or on the heat exchange surface second side 114). Insuch aspects, there can be level of liquid phase of the heat exchangemedium within first heat exchanger 111 (or on the heat exchange surfacesecond side 114).

The heat exchange system 110 can further comprise a level indicatorand/or controller 140 configured to measure, monitor, and/or control alevel of the liquid phase of the first heat exchange medium in the firstheat exchanger 111 (or on the heat exchange surface second side 114).Generally, the level indicator and/or controller 140 is coupled to theheat exchanger 211. In an aspect, the level indicator and/or controller140 can include 1) one or more pressure drop (DP) cells (fluidlyconnected to process line 201 and/or fluidly connected to process line202), not shown, configured to measure the pressure drop across the heatexchange surface second side 114 (also referred to as the pressure dropacross the heat exchange surface second side 114 of heat exchanger 111);2) a pressure sensor (not shown) on the heat exchange medium inlet sideof the heat exchanger 111 (e.g., in or fluidly connected to process line201), a pressure sensor (not shown) on the heat exchange medium outletside of the heat exchanger 111 (e.g., in or fluidly connected to processline 202), and a device (not shown) to calculate the pressure dropacross the heat exchange surface second side 114; and/or 3) atemperature sensor (not shown) on the heat exchange medium inlet side ofthe heat exchanger 111 (e.g., in process line 201), a temperature sensor(not shown) on the heat exchanger outlet side of the heat exchanger 111(e.g., in process line 202), and device (not shown) to convert thetemperature readings to pressure and calculate the pressure drop acrossthe heat exchange surface second side 114 of heat exchanger 111. Thepressure drop across the heat exchange surface second side 114 can besubsequently utilized to determine the equivalent amount of heatexchange medium (or the equivalent height, or a liquid level, of theheat exchange medium) on the heat exchange surface second side 114 atstill conditions (i.e., conditions at which there are no bubbles). Thepressure drop across the heat exchange surface second side 114 can beutilized to determine the level of liquid phase of heat exchange mediumin the heat exchanger 111 (or on the heat exchange surface second side114). Lines 141 and 142 represent fluid lines to fluidly connect processlines 201 and 202 to level controller 140 and electrical lines orwireless transmitters to transmit pressure and/or temperature readings,to level controller 140. In some aspects, the level indicator and/orcontroller 140 can be configured to actuate one or more control valves(not shown) to control the flow rate of the heat exchange medium (liquidphase and/or vapor phase) into or out of heat exchanger 11 (e.g., viacontrol valves—not shown—on process lines 201 and/or 202);alternatively, or additionally, the level controller 140 can beconfigured to actuate one or more control valves (not shown) to controlthe flow of the reaction mixture (or components for the reactionmixture) into heat exchanger 111 (e.g., via process line 102);additionally or alternatively, the level indicator and/or controller 140can be configured to actuate one or more heat exchange medium flowcontrol valves to control the first level of liquid phase of the firstheat exchange medium on the first heat exchange surface second side 114.In an aspect, level indicator and/or controller 140 can be configured tocontrol the first level of liquid phase of the first heat exchangemedium of the first heat exchange surface first side to be a) anypercentage of the at least a portion of the reaction mixture on thefirst heat exchange surface first side which indirectly contacts aliquid phase of the first heat exchange medium on the first heatexchange surface second side disclosed herein, b) any percentage of thesurface area of the first heat exchange surface second side whichcontacts the liquid phase of the first heat exchange medium disclosedherein, c) any volume ratio of the liquid phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) to the vapor phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) disclosed herein, or d) any combinationthereof.

Heat exchange system 110 of reaction system 100 in FIG. 1 can furthercomprise one or more pressure controllers (e.g., pressure controller 130and a pressure control device 131) in fluid communication with the heatexchange surface second side 114 (e.g. through at least one of theprocess lines 201 and/or 202 (shown)). The one or more pressurecontrollers can be configured to measure, monitor, and/or control thepressure of less than 1 atmosphere (101.3 kPa) on the first heatexchange surface second side. The level indicator and/or controller(coupled to the first heat exchanger) is configured to control the firstlevel of liquid phase of the first heat exchange medium of the firstheat exchange surface first side to be a) any percentage of the at leasta portion of the reaction mixture on the first heat exchange surfacefirst side which indirectly contacts a liquid phase of the first heatexchange medium on the first heat exchange surface second side disclosedherein, b) any percentage of the surface area of the first heat exchangesurface second side which contacts the liquid phase of the first heatexchange medium disclosed herein, c) any volume ratio of the liquidphase of the first heat exchange medium in the first heat exchanger (oron the first heat exchange surface second side) to the vapor phase ofthe first heat exchange medium in the first heat exchanger (or on thefirst heat exchange surface second side) disclosed herein, or d) anycombination thereof. Pressure control device 130 can be fluidlyconnected to process line 202 by process line 107. In an aspect, thepressure controller 130 and pressure control device 131 (and optionallyprocess line 107) are fluidly connected to the process line 202 and areconfigured to provide to apply any pressure of less than 1 atmosphere(101.3 kPa) described herein on the first heat exchange surface secondside 114 (or on the heat exchange medium). In another aspect, pressurecontrol device 130 and pressure control device 131 (and optionallyprocess line 107) can be utilized to 1) control the pressure on the heatexchange surface second side 114 (or on the heat exchange medium), 2)control the level of liquid phase of the heat exchange medium on theheat exchange surface second side, 3) control the reaction mixturetemperature (or average reaction mixture temperature) on the heatexchange surface first side, 4) any combination thereof. Pressurecontrol device 131 can include a pressure sensor (not shown) in, orfluidly connected to, process line 202 (or process line 201) andconfigured to 1) receive pressure measurement signals from the pressuresensor and 2) perform control logic to allow pressure control device 130to control the pressure on the heat exchange surface second side 114 (oron the heat exchange medium);

Reaction system 100 in FIG. 1 can further comprise a temperatureindicator and/or controller (not shown) configured to measure and/orcontrol the reaction mixture temperature (or average reaction mixturetemperature) within the reaction zone 101. In an aspect, the temperatureindicator and the temperature controller functions can be contained in asingle device or in separate devices; alternatively, a single device, oralternatively, in separate devices. In an aspect, the temperatureindicator and/or controller can be a) coupled to at least one of thepressure control devices (e.g., pressure controller 130 and a pressurecontrol device 131) and configured to actuate a control mechanism tocontrol a pressure set point of the at least one of the one or morepressure control devices, b) coupled with the level indicator orcontroller 140 and configured to control the level of liquid phase ofthe heat exchange medium in the first heat exchanger (or on the heatexchange surface second side, c) coupled to the heat exchange mediumflow control valve (not shown) and configured to actuate a heat exchangemedium flow control valve to control the flow rate of liquid phase ofthe first heat exchange medium into the first heat exchange surfacesecond side, or d) a combination thereof, in response to the reactionmixture temperature (or average reaction mixture temperature).

The temperature of the reaction mixture within the reaction zone 101 iscontrolled (maintained, increased, or decreased) according to thetechniques disclosed herein. In aspects, the temperature and/or pressureof the heat exchange system (e.g., the heat exchange medium, the heatexchanger 111 in FIG. 1 , and optionally any combination of other heatexchange components discussed for FIG. 2 or 3 ) can be controlled toprovide any reaction mixture temperature (or average reaction mixturetemperature) in the reaction zone 101 as described. Control of thetemperature and pressure of the heat exchange system are described inmore detail herein.

The reaction mixture temperature (or average reaction mixturetemperature) within the reaction zone 101 of the reaction process andreaction system 100 can be controlled (maintained, increased ordecreased) by continuously or intermittently introducing the heatexchange medium into the heat exchanger 111 via line 201 andcontinuously or intermittently removing the heat exchange medium fromthe heat exchanger 111 via line 202, while the reaction mixture contactsthe first heat exchange surface first side 113 and passes through theheat exchanger 111. The techniques contemplated by the disclosure forcontrolling the temperature of the reaction mixture are described inmore detail herein. Generally, the transfer of heat within the heatexchanger 111 occurs because heat transfers through the heat exchangesurface 112 from the reaction mixture into the heat exchange medium, orvice versa. In aspects where heat transfers from the reaction mixture tothe heat exchange medium via the heat exchange surface 112 (e.g., duringthe exothermic oligomerization reactions), the reaction mixture iscooled by transferring heat to the heat exchange surface 112 and theheat exchange medium is heated warmed by transferring heat from the heatexchange surface 112. In aspects where heat transfers from the heatexchange medium to the reaction mixture via the heat exchange surface112, the heat exchange medium is cooled by transferring heat to the heatexchange surface 112 and the reaction mixture is warmed by transferringheat from the heat exchange surface 112. Consequently, the heatexchanger and heat exchange medium maintain a desired temperature bycooling the portions of the reaction mixture that are hotter than theheat exchange medium and/or heating the portions of the reaction mixturewhich are cooler than the heat exchange medium. Additionally, the heatexchange can be utilized to increase or decrease the desired reactiontemperature by changing the temperature of the heat exchange mediumwithin the heat exchanger (e.g., via controlling the pressure on thefirst heat exchange surface second side 114).

FIG. 2 illustrates a portion of another non-limiting reaction system,reaction system 200, including a heat exchange system 210 and at least aportion of reaction zone 101. In an aspect, heat exchange system 210 canbe utilized to control a reaction mixture temperature (or an averagereaction mixture temperature) within reaction zone 101 and/or a pressurein the heat exchange system. The reaction system 200 of FIG. 2 issimilar to reaction system 100 of FIG. 1 , wherein like numbersrepresent like components described in relation to FIG. 1 and theirdescriptions and/or functions can be utilized to further describereaction system 200 and/or heat exchange system 210 without limitationunless explicitly indicated. The heat exchange system 210 in FIG. 2differs from the heat exchange system 110 in FIG. 1 in that heatexchange system 210 includes a second heat exchanger 211 and processlines 203 and 204. Additionally, heat exchange system 210 in FIG. 2differs from the heat exchange system 110 in FIG. 1 in that the heatexchange medium is circulated in a heat exchange medium loop includingheat exchanger 111 and second heat exchanger 211. The unique aspects ofreaction system 200 and heat exchange system 210 are discussed in moredetail herein. Reaction system 200 and heat exchange system 210 canadditionally comprise any equipment associated with reaction systems,such as a vessel, one or more control devices (e.g., a PID controller),measurement instruments (e.g., thermocouples, transducers, and flowmeters), alternative inlet lines, and outlet lines (all not shown).

The second heat exchanger 211 is configured to provide indirect contactbetween the heat exchange medium discussed for FIG. 1 and a second heatexchange medium. Indirect contact refers to contact through a heatconductive material such as the second heat exchange surface 212described herein (e.g., a second heat exchange surface which can beembodied as such as metal tubes or metal plates), without any directcontact or mixing between the two heat exchange mediums. The second heatexchanger 211 comprises second heat exchange surface 212 (distinct fromthe heat exchange surface 112) that is configured to separate the firstheat exchange medium from the second heat exchange medium inside theheat exchanger 211 and thus provide indirect contact between the twoheat exchange mediums. Heat exchange surface 212 thus separates the heatexchanger 211 into two sections: a first section through which the firstheat exchange medium flows and a second section through which the secondheat exchange medium flows. In aspects, the second heat exchanger 211comprises a second heat exchange surface first side 213 (i.e., firstside 213 of the second heat exchange surface 212) configured to contactthe first heat exchange medium and a second heat exchange surface secondside 214 (i.e., second side of the second heat exchange surface 212)configured to contact the second heat exchange medium. In an aspect, apressure on the second heat exchange surface first side 213 can be anypressure less than 1 atmosphere (101.3 kPa) as disclosed herein. In anaspect, the second heat exchange surface does not contact the reactionmixture. In an aspect, the second heat exchange surface 212 can behorizontally oriented, e.g., embodied as horizontally oriented tubes orplates, or vertically oriented, e.g., embodied as vertically orientedtubes or plates; alternatively, horizontally oriented; or alternatively,vertically oriented. In an aspect, the pressure in the heat exchangesystem 210 that is controlled can be the pressure on the first heatexchange surface first side 113 and the pressure on the second heatexchange surface second side 214 (or on the first heat exchange medium).

The second heat exchange medium inflow line 203 and the second heatexchange medium outflow line 204 are connected to the second heatexchanger 211. The second heat exchange medium can flow into the secondheat exchanger 211 via inflow line 203 configured to allow for flow ofthe second heat exchange medium into heat exchange 211, and throughsecond heat exchanger 211 where the second heat exchange medium contactsthe second heat exchange surface second side 214. Heat is indirectlytransferred from the first heat exchange medium to the second heatexchange medium via contact of first heat exchange medium with thesecond heat exchange surface first side 213 and by contacting the secondheat exchange medium with the second heat exchange surface second side214. Flow of the second heat exchange medium through the second heatexchanger 211 carries heated second heat exchange medium out of thesecond heat exchanger via outflow line 204 configured to allow for flowof the second heat exchange medium out of second heat exchanger 211.

The direction of flow of the first heat exchange medium relative to thedirection of flow of the second heat exchange medium in the second heatexchanger 211 can be counter flow, concurrent flow, cross flow, or acombination thereof. In an aspect, the second heat exchange surface 212can include multiple passes where the first heat exchange mediumindirectly contacts the second heat exchange medium. In aspects, thesecond heat exchanger 211 can be of a tubular design (e.g., shell andtube heat exchanger), a plate design (e.g., shell and plate heatexchanger), or a combination of tubular and plate design; alternatively,tubular design; alternatively, a plate design; or alternatively, acombination of tubular and plate design. In any design, the second heatexchange surface 212 can be embodied as a tube and/or plate configuredto provide the indirect contact between the first heat exchange mediumand the second heat exchange medium. It is contemplated that the firstheat exchange medium can flow on the tube side or plate side of thesecond heat exchanger 211 while the second heat exchange medium flows onthe shell side; alternatively, the first heat exchange medium can flowon the shell side while the second heat exchange medium can flow on thetube side or plate side.

The second heat exchanger 211 of the heat exchange system 210 is fluidlyconnected to the first heat exchanger 111 by a plurality of conduits(e.g., process line 201 and process line 202). In FIG. 2 , process lines201 and 202 each represent a conduit of the plurality of conduits andare configured to fluidly connect the first heat exchanger 111 and thesecond heat exchanger 112 and configured to allow for flow of the firstheat exchange medium between the first heat exchange surface second side114 and the second heat exchange surface first side 113. The pluralityof conduits (e.g., process lines 201 and 202), the first heat exchanger111, and the second heat exchanger 211 are configured to fluidly connectthe first heat exchanger and the second heat exchanger to form a firstheat exchange medium circulation loop circulation loop. In thecirculation loop, the first heat exchange medium can flow between theheat exchange surface second side 114 and the second heat exchangesurface first side 213. In an aspect, at least one of one or moreconduits (e.g., process line 202) allows for flow of the first heatexchange medium from the heat exchange surface second side 114 (alsoreferred to herein as the first heat exchange surface second side 114for clarity) to the second heat exchange surface first side 213, and atleast one of the one or more conduits (e.g., process line 201) allowsfor flow of the first heat exchange medium from the second heat exchangesurface first side 213 to the first heat exchange surface second side114.

In aspects where the heat exchange system contains both liquid phase andvapor phase of the first heat exchange medium, the heat exchange system210 can be configured such that the vapor phase of the first heatexchange medium condenses to liquid phase first heat exchange medium inthe second heat exchanger 211. In an aspect, the first heat exchangemedium enters the second heat exchanger 211 through line 202 as vaporphase, and the first heat exchange medium contacts the second heatexchange surface first side 213, and ultimately condenses into liquidphase first heat exchange medium. Thus, vapor phase and liquid phase ofthe first heat exchange medium can contact the second heat exchangesurface first side 213. As such, at least a first part of the secondheat exchange medium on the second heat exchange surface second side 214(or a first part of the surface area of the second heat exchange surfacefirst side) indirectly contacts the vapor phase of the first heatexchange medium on the second heat exchange surface first side 213 and asecond part of the second heat exchange medium on the second heatexchange surface second side 214 indirectly contacts liquid phase of thefirst heat exchange medium on the second heat exchange surface firstside 213. Thus, there is provided a second level of first heat exchangemedium on the second heat exchange surface first side. In an aspect, atleast one of the plurality of conduits (e.g., process line 202) allowsfor flow of the vapor phase of the first heat exchange medium from thefirst heat exchanger (or the first heat exchange surface second side114) to the second heat exchanger (or second heat exchange surface firstside 213), and at least one of the plurality of conduits (e.g., processline 201) allows for flow of the liquid phase of first heat exchangermedium from the second heat exchanger (or the second heat exchangesurface first side 213) to the first heat exchange (or the first heatexchange surface second side 114).

In an aspect, vapor phase and liquid phase of the first heat exchangemedium can be present in the second heat exchanger 211 (or on/contactingthe second heat exchange surface first side 213). In such aspects, therecan be level of liquid phase of the heat exchange medium within secondheat exchanger 211 (or on/contacting the second heat exchange surfacefirst side 213). The level of liquid phase of the heat exchange mediumwithin first heat exchanger 211 (or on/contacting the second heatexchange surface first side 213) can also be referred to herein as asecond level of liquid phase of the first heat exchange medium forclarity to distinguish it from the level of liquid phase of the firstheat exchange medium on the first heat exchange surface second side 114,which can also be referred to herein as the first level of the liquidphase of the first heat exchange medium. The second level of liquidphase of the first heat exchange medium can be i) any percentage of thesecond heat exchange medium on the second heat exchange surface secondside 214 which indirectly contacts the liquid phase of the first heatexchange medium on the second heat exchange surface first side 213disclosed herein, ii) any volume ratio of the liquid phase of the firstheat exchange medium in the second heat exchanger 211 (or on the secondheat exchange surface first side 213) to the vapor phase of the firstheat exchange medium in the second heat exchanger 211 (or on the secondheat exchange surface first side 213) disclosed herein, or iii) anycombination thereof. The disclosure contemplates monitoring and/orcontrolling the second level of the liquid phase of the first heatexchange medium in the second heat exchanger 211 (or on/contacting thesecond heat exchange surface first side 213). In some aspects, thesecond level of the liquid phase of the first heat exchange medium onthe second heat exchange surface first side 213 can be utilized tocontrol pressure on the first heat exchange surface second side 114 (oron the second heat exchange surface first side 213 or on the first heatexchange medium) and/or control the reaction mixture temperature (or theaverage reaction mixture temperature). Techniques for controlling thesecond level of liquid phase of the first heat exchange medium in thesecond heat exchanger (or on/contacting the second heat exchange surfacefirst side 213) are described in more detail herein. In an aspect, thefirst heat exchange medium on the second heat exchange surface firstside 213 can be on the shell side of the second heat exchanger 211, oron the tube or plate side of the second heat exchanger 211;alternatively, on the shell side of the second heat exchanger 211; oralternatively, on the tube or plate side of the second heat exchanger211.

As in FIG. 1 , the heat exchange system 210 of reaction system 200depicted in FIG. 2 can further comprise one or more pressure controllers(e.g., pressure controller 130 and pressure control device 131) and canhave the general features (e.g., a pressure sensor, not shown, amongother features) and/or functions (e.g., receive pressure measurementsignals and/or control a pressure, among other functions) of the one ormore pressure controllers as disclosed for FIG. 1 . The one or morepressure controllers depicted in FIG. 2 differ from the one or morepressure controllers in FIG. 1 in the aspect that the one or morepressure controllers can be in fluid communication with the first heatexchange surface second side 114 and/or the second heat exchange surfacefirst side 213. In an aspect, the one or more pressure controllers(e.g., pressure controller 130 and a pressure control device 131) can bein direct fluid communication with at least one of the plurality ofconduits (e.g., process line 201 or 202), for example via process line107. In one aspect, the one or more pressure controllers (e.g., pressurecontroller 130 and a pressure control device 131) can be in direct fluidcommunication with at least one of the plurality of conduits allowingfor flow of the first heat exchange medium from the first heat exchangesurface second side 114 to the second heat exchange surface first side213 (e.g. process line 202), for example via process line 107. Inanother aspect, the one or more pressure controllers (e.g., pressurecontroller 130 and a pressure control device 131) can be in direct fluidcommunication with at least one of the plurality of conduits allowingfor flow of the vapor phase of the first heat exchange medium from thefirst heat exchange surface second side 114 to the second heat exchangesurface first side 213 (e.g. process line 202), for example via processline 107. The one or more pressure controllers (e.g., pressurecontroller 130 and a pressure control device 131) can be configured tomeasure, provide, and/or control the pressure on the first heat exchangesurface second side 114 and/or the second heat exchange surface firstside 213. Generally, the one or more pressure controllers (e.g.,pressure controller 130 and a pressure control device 131) can provide,and/or control, the pressure to be any pressure less than 1 atmosphere(101.3 kPa) disclosed herein. Additionally, the one or more pressurecontrollers of FIG. 2 (e.g., pressure controller 130 and a pressurecontrol device 131) can differ from the one or more pressure controllersof FIG. 1 in that at least one of the one or more controllers of FIG. 2can have an outlet line (e.g., outlet line 109). In an aspect, outletline 109 can assist in allowing the one or more pressure controllers toprovide, and/or control the pressure on the first heat exchange surfacesecond side 114 and/or the second heat exchange surface first side 213(and/or the first heat exchange medium). In another combinable aspect,at least one of the one or more pressure controllers can include asensor (not shown) and/or a control valve (not shown) within thepressure controller or outline line 109. In an aspect, the sensor can beconfigured to actuate the control valve between an open position and aclosed position to 1) control the pressure on the first heat exchangesurface second side 114 and/or the second heat exchange surface firstside 213, and/or 2) allow non-condensable components in the first heatexchange medium to be removed from the first heat exchange medium (orfrom the first heat exchange medium circulation loop).

As in FIG. 1 , the heat exchange system 210 of reaction system 200depicted in FIG. 2 can further comprise a level indicator and/orcontroller 140 configured to measure, monitor, and/or control a level ofthe liquid phase of the first heat exchange medium in the first heatexchanger 111 (or on the heat exchange surface second side 114) and canhave the general features (e.g., pressure drop cells, pressure sensors,and associated devices) to calculate pressure drop across the heatexchange surface second side 114. And/or the system 210 can furthercomprise a temperature sensor and device (not shown) to convert thetemperature readings to pressure and calculate the pressure drop acrossthe heat exchange surface second side 114 of heat exchanger 111, amongother features and/or functions (e.g., control the flow of the reactionmixture (or reaction mixture components) into heat exchanger 111 and/orcontrol the level of liquid phase of the first heat exchange medium onthe first heat exchange surface second side 114, among other functions)of level indicator and/or controller 140 as disclosed for FIG. 1 .

Reaction system 200 in FIG. 2 , similar to FIG. 1 , can further comprisea temperature indicator and/or controller (not shown) configured tomeasure and/or control the reaction mixture temperature (or averagereaction mixture temperature) within the reaction zone 101. In anaspect, the temperature indicator and/or controller can be a) coupled toat least one of the pressure control devices (e.g., pressure controller130 and a pressure control device 131) and configured to actuate acontrol mechanism to control a pressure set point of the at least one ofthe one or more pressure control devices, b) coupled with the firstlevel indicator or controller 140 and configured to control the level ofliquid phase of the heat exchange medium in the first heat exchanger (oron the heat exchange surface second side, or c) a combination thereof,in response to the reaction mixture temperature (or average reactionmixture temperature).

In an aspect, the second heat exchanger 211 can be vertically higherrelative to a common reference point 221 (not shown) on the ground 220(not shown) than the first heat exchanger 111. Generally, verticallyhigher can be a vertical distance H. The minimum distance H can be 0.05,0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4,1.5, 1.6, 1.7, 1.8, 1.9, or 2.0 meters; or additionally, a maximum of15, 12, 10, 8, 7, 6, 5, 4, 3, 2, or 1 meter. In an aspect, the distanceH can range from any minimum value disclosed herein to any maximum valuedisclosed herein. Non-limiting suitable ranges for the distance H caninclude from 0.05 meters to 15 meters, 0.1 meters to 10 meters, 0.1meters to 5 meters, 0.2 meters to 10 meter, 0.2 meters to 5 meters, 0.2meters to 2 meters, 0.3 meters to 5 meters, 0.3 meters to 2 meters, 0.5meters to 5 meters, 0.5 meters to 2 meters, 0.7 meters to 10 meters, 0.7meters to 5 meters, and 1 meter to 5 meters. Other appropriate distancesH are readily apparent from this disclosure. In one aspect, verticallyhigher relative to a common point of reference can mean the bottom 215of the second heat exchanger 211 can be vertically higher than the top115 of the first heat exchanger 111. In another aspect, verticallyhigher relative to a common reference point on the ground can mean thatthe second level of the liquid phase of the first heat exchange mediumin the first heat exchanger 211 (or on/contacting the second heatexchange surface first side 213) is vertically higher relative to acommon reference point on the ground than the first level of the liquidphase of the first heat medium in the first heat exchanger (oron/contacting the first heat exchange surface second side 114). Withoutbeing limited by theory, it is believed that having a vertical distance,H, between the bottom 215 of the second heat exchanger 211 and the top115 of the first heat exchanger 111, or between the first level ofliquid phase of the first heat exchange medium and the second level ofliquid phase of the first heat exchange medium, can be advantageous incontrolling the pressure on the first heat exchange surface second side14 and/or on second heat exchange surface first side 213 (and/or on thefirst heat exchange medium).

FIG. 3 illustrates a portion of another non-limiting reaction system,reaction system 300, including a heat exchange system 310, and at leasta portion of reaction zone 101. In an aspect, heat exchange system 310can be utilized to control a reaction mixture temperature (or an averagereaction mixture temperature) within reaction zone 101, and/or apressure in the heat exchange system. Reaction system 300 of FIG. 3 issimilar to reaction system 100 of FIG. 1 and reaction system 200 of FIG.2 , wherein like numbers represent like components described in relationto FIG. 1 and/or FIG. 2 and their descriptions and functions can beutilized to further describe reaction system 300 and/or heat exchangesystem 310 without limitation unless explicitly indicated. The heatexchange system 310 in FIG. 3 differs from the heat exchange system 210in FIG. 2 in that heat exchange system 310 includes various equipmentand streams for 1) monitoring and/or controlling a reaction mixturetemperature (or average reaction mixture temperature) in the reactionzone 101, a pressure in the heat exchange system 310 (or on the firstheat exchange medium), and amount of the first heat exchange medium inthe heat exchange system 310. Similar to heat exchange system 210 ofFIG. 2 , heat exchange system 310 in FIG. 3 includes the first heatexchanger 111, process lines 201 and 202, the second heat exchanger 211,and process lines 203 and 204, level controller 140 and associateprocess lines 142 and 141, pressure controller 130, pressure controldevice 131, and associated process lines 107 and 109, among otherequipment and process lines disclosed for heat exchange system 210.Similar to the heat exchange system 210 described for FIG. 2 , the firstheat exchange medium in heat exchange system 310 in FIG. 3 is circulatedin a heat exchange medium loop including the first heat exchanger 111,process lines 201 and 201, and the second heat exchanger 211. Reactionsystem 300 and heat exchange system 310 in FIG. 3 depict furtherequipment for 1) monitoring and/or controlling a reaction mixture (oraverage reaction mixture) temperature, 2) monitoring and/or controllinga temperature (or average temperature) of the first heat exchange mediumthroughout heat exchange system 310, 3) monitoring and/or controlling apressure on the first heat exchange surface second side 114 (or on thesecond heat exchange surface first side 213 and/or the first heatexchange medium), and/or 4) adding first heat exchange medium to, orremoving first heat exchange medium from, the first heat exchange mediumcirculation loop, or 5) any combination thereof. The unique aspects ofreaction system 300 and heat exchange system 310 are discussed in moredetail herein. Reaction system 300 and heat exchange system 310 canadditionally comprise any equipment associated with reaction systems,such as a vessel, one or more control devices (e.g., a PID controller),measurement instruments (e.g., thermocouples, transducers, and flowmeters), alternative inlet lines, and outlet lines (all not shown). Ascan be seen in FIG. 3 , the heat exchange system 310 can differ fromheat exchange system 210 in that heat exchange system can furthercomprise a first heat exchange medium inlet line 301 and a first heatexchange medium outlet line 305. The first heat exchange medium inletand outlet lines are fluidly connected at least one of the plurality ofconduits of the first heat exchange medium circulation loop. In anaspect, the first heat exchange medium inlet and outlet lines arefluidly connected to the at least one of the plurality of inletsallowing for flow of the first heat exchange medium from the second heatexchanger 211 (or from the second heat exchange surface first side 213)to the first heat exchanger 111 (or the first heat exchange surfacesecond side 114 (e.g., process line 201). The first heat exchange mediuminlet line 301 can be configured to introduce first heat exchange mediuminto the first heat exchange medium circulation loop (e.g., via processline 201) while the first heat exchange medium outlet 305 can beconfigured to remove a portion of the first heat exchange medium fromthe first heat exchange medium circulation loop (e.g., via process line201). Heat exchange system 311 can further comprise a first controlvalve 302 located on the first heat exchange fluid inlet line 301 and asecond control valve 306 located on the first heat exchange mediumoutlet line 305. The first control valve 302 can be configured tocontrol (allow or disallow) the addition of first heat exchange mediumto the first heat exchange medium circulation loop (e.g., via processline 201) while the second control valve is configured to control (allowor disallow) the removal of first heat exchange medium from the firstheat exchange medium circulation loop (e.g., via process line 201). Inan aspect, first heat exchange medium added to the first heat exchangemedium circulation loop via first heat exchange fluid inlet line 301 canbe in the liquid phase or vapor phase; alternatively, liquid phase; oralternatively, vapor phase. While FIG. 3 depicts outlet line 305 at alocation between the first inlet line 301 and the first heat exchanger111 (or the first heat exchange surface second side 114), it iscontemplated that the outlet line 301 can be located at any positionbetween the first heat exchanger 111 (or the first heat exchange surfacesecond side 114) and second heat exchanger 211 (or the second heatexchange surface first side 213) on the process line 201 allowing forflow of the first heat exchange medium from the second heat exchanger211 (or form the second heat exchange surface first side 213) to thefirst heat exchange 111 (or to the first heat exchange surface secondside 114). Thus first heat exchange medium outlet line can be located ata position between the second heat exchanger 211 (or the second heatexchange surface first side 213) and the first heat exchange mediuminlet line 301 on the process line 201 allowing for flow of the firstheat exchange medium from the second heat exchanger 211 (or form thesecond heat exchange surface first side 213) to the first heat exchange111 (or to the first heat exchange surface second side 114). While FIG.3 depicts only one inlet line and outlet line with their correspondingcontrol values, it is contemplated that there can be more than one inletvalve for introducing first heat exchange medium to the first heatexchange medium circulation loop and/or more than one outlet line forremoving heat exchange medium from the first heat exchange mediumcirculation loop. Thus, additional first heat exchange medium inlet andoutlet lines can be accordingly added to achieve a particular reactionsystem and/or heat exchange system purpose. These additional first heatexchange medium inlet lines and/or outlet lines can each have their ownindependent control values.

The first control valve 302 and the second control valve 306 can becoupled to the level indicator 140 (also referred to herein as firstlevel indicator and/or controller 140 to differentiate it from secondlevel controller indicator and/or controller 350). In an aspect, thefirst level indicator and/or controller 140 can be configured to (a)actuate the first control valve 302 to an open position to add firstheat exchange medium to the heat exchange system (or the first heatexchange medium circulation loop), and/or (b) actuate the second controlvalve 306 to an open position to remove a portion of the first heatexchange medium from the first heat exchange medium circulation. Signalsfrom level controller 140 and/or control logic can be utilized toactuate control valve 302 and/or control value 306 to allow or disallowflow of liquid phase of the first heat exchange medium into or out ofthe circulation loop to provide and/or control (maintain, adjust,increase and/or decrease) the desired first level of liquid phase or thefirst heat exchange medium on the first heat exchange surface secondside 114. The actuation of the first control valve 302 and/or the secondcontrol valve 306 can be performed so as to provide and/or control adesired first level of liquid phase of the heat exchange medium withinfirst heat exchanger 211 (or on the first heat exchange surface secondside 114). The actuation of the first control valve can be utilized inincrease the first level of liquid phase of the first heat exchangemedium in the first heat exchanger 111 (or on the first heat exchangesurface second side 114). The actuation of the second control valve canbe utilized to decrease the first level of liquid phase of the firstheat exchange medium in the first heat exchanger 111 (or on the firstheat exchange surface second side 114). The desired first level ofliquid phase of the first heat exchange medium can be any value of thefirst level of liquid phase of the first heat exchange medium disclosedherein as provided in any terms of first level of liquid first heatexchange medium as disclosed herein. The control valves of anyadditional first heat exchange medium inlet lines and/or outlet linescan also be coupled to, and/or actuated by, the first level indicatorand/or controller 140.

In an aspect, the heat exchange system can include a separate vaporphase of the first heat exchange medium inlet line (not shown) fluidlyconnected to at least one of the plurality of conduits of the first heatexchange medium circulation loop. In an aspect, the vapor phase of thefirst heat exchange medium inlet (not shown) can be fluidly connected tothe at least one of the plurality of inlets allowing for flow of thefirst heat exchange medium from the second heat exchange 211 (or fromthe second heat exchange surface first side 213) to the first heatexchanger 111 (or the first heat exchange surface second side 114 (e.g.,process line 201). The heat exchange system can further include acontrol valve (not shown) located on the vapor phase of the first heatexchange fluid inlet line and configured to actuate between an openposition and a closed position so as to allow or disallow a flow ofvapor phase of the first heat exchange medium into the first heatexchange medium circulation loop. In an aspect, the introduction ofvapor phase of the first heat exchange medium into the first heatexchange medium circulation loop can be utilized to heat up the firstheat exchange medium circulation loop prior to initiation the olefinoligomerization and/or to increase the temperature of the first heatexchange medium entering the first heat exchanger 111 (or contacting thefirst heat exchange surface second side 114).

As seen in FIG. 3 , heat exchange system 310 can differ from heatexchange system 210 in that heat exchange system 310 can furthercomprise a second level indicator and/or controller 350. Generally, thesecond level indicator and/or controller 350 is coupled to the secondheat exchanger 211. In an aspect, the level controller 350 caninclude 1) one or more pressure drop (DP) cells (fluidly connected toprocess line 202 and/or fluidly connected to process line 201) measuringthe pressure drop across the second heat exchange medium surface firstside 213 (also referred to as the pressure drop across the second heatexchange surface first side 213), 2) a pressure sensor on the heatexchange medium inlet side of the heat exchanger 211 (e.g., in orfluidly connected to process line 202), a pressure sensor on the heatexchange medium outlet side of the heat exchanger 211 (e.g., in orfluidly connected to process line 201), and a device to calculate thepressure drop across the second heat exchange surface first side 213,and/or 3) a temperature sensor on the heat exchange medium inlet side ofthe heat exchanger 211 (e.g., in process line 202), a temperature sensoron the heat exchanger outlet side of the heat exchanger 211 (e.g., inprocess line 201), and device to convert the temperature readings topressure and calculate the pressure drop across the second heat exchangesurface first side 213. The pressure drop across the second heatexchange surface first side 213 can be subsequently utilized todetermine the equivalent amount of heat exchange medium (or theequivalent height, or a liquid level, of heat exchange medium) on thesecond heat exchange surface first side 213 at still conditions (i.e.,conditions at which there are no bubbles). The pressure drop across thesecond heat exchange surface first side 213 can be utilized to determinethe second level of liquid phase of heat exchange medium in the heatexchanger 211 (or on the second heat exchange surface first side 213).Lines 351 and 352 represent fluid lines to fluidly connect process lines201 and 202 to level controller 350, or electrical lines or wirelesstransmitters to transmit pressure and/or temperature readings, to levelcontroller 350. In an aspect, second level indicator and/or controller350 can be configured to measure, monitor, and/or control (maintain,adjust, increase, decrease) the second level of the first heat exchangemedium in the second heat exchanger 211 (or on the second heat exchangesurface first side 213). In an aspect, the second level indicator and/orcontroller 350 can be configured to control the second level of liquidphase of the first heat exchange medium of the second heat exchangesurface first side to be i) any percentage of the second heat exchangemedium on the second heat exchange surface second side 214 whichindirectly contacts the liquid phase of the first heat exchange mediumon the second heat exchange surface first side 213 disclosed herein, ii)any volume ratio of the liquid phase of the first heat exchange mediumin the second heat exchanger 211 (or on the second heat exchange surfacefirst side 213) to the vapor phase of the first heat exchange medium inthe second heat exchanger 211 (or on the second heat exchange surfacefirst side 213) disclosed herein, or iii) any combination thereof.

Heat exchange system 310, in comparison to heat exchange system 210, canfurther comprise an optional temperature indicator and/or controller323. In an aspect, the temperature indicator and the temperaturecontroller functions of temperature indicator and/or controller 323 canbe contained in a single device or in separate devices; alternatively, asingle device, or alternatively, in separate devices. In an aspect,optional temperature indicator 323 can be can be fluidly connected to,or located within, at least one of the plurality of conduits allowingfor flow of liquid phase of the first heat exchange medium from thesecond heat exchanger 211 (or from the second heat exchange surfacefirst side 213) to the first heat exchanger 111 (or the first heatexchange surface second side 114, e.g., process line 201. Optionaltemperature indicator 323 can be configured to measure and/ordisplay/transmit the heat exchange medium temperature in process line201. In an aspect optional temperature indicator 323 can be configuredto control the second level of liquid phase of the first heat exchangemedium in the second heat exchanger 211 (or on the second heat exchangesurface first side 213), the first level of liquid phase of the firstheat exchange medium in the first heat exchanger (or on the first heatexchange surface second side 114), and/or the pressure on the first heatexchange surface second side 114 (and/or second heat exchange surfacefirst side 213, and/or first heat exchange medium).

Heat exchange system 310, in comparison to heat exchange system 210, canfurther comprise a liquid control valve 308. Liquid control valve 308can be located on at least one of the plurality of conduits allowing forflow of the first heat exchange medium from the second heat exchanger211 (or from the second heat exchange surface first side 213) to thefirst heat exchanger 111 (or the first heat exchange surface second side114). Liquid control valve 308 can be configured to control a secondlevel of the liquid phase of the first heat exchange medium in thesecond heat exchanger 211 (or on the second heat exchange surface firstside 213). In an aspect, liquid control valve 308 can be configured tocontrol the second level of liquid phase of the first heat exchangemedium in the second heat exchanger 211 (or on the second heat exchangesurface first side 213), the first level of liquid phase of the firstheat exchange medium in the first heat exchanger (or on the first heatexchange surface second side 114), and/or the pressure on the first heatexchange surface second side 114 (and/or second heat exchange surfacefirst side 213, and/or first heat exchange medium).

Level controller 350 and/or the optional temperature indicator and/orcontroller 323 can be utilized to control the second level of the liquidphase of the first heat exchange medium in the second heat exchanger 211(or on the second heat exchange surface first side 213). Thus, in anaspect, level controller 350 and/or the optional temperature indicatorand/or controller 323 can be coupled to 1) the liquid control valve 308and configured to actuate liquid control vale 308 to control the flow ofthe second heat exchange medium from the second heat exchanger 211 (oron the second heat exchange surface first side 213) to the first heatexchanger 111 (or the first heat exchange surface second side 214), 2) asecond heat exchange medium flow valve (located on second heat exchangeinlet line 203 (not shown) or second heat exchange outlet line 204 (notshown)) configured to actuate the second heat exchange medium flowcontrol valve (not shown) to control the flow rate of the second heatexchange medium into (or out of) the second heat exchanger 211 (contactwith the second heat exchange surface second side 214), or 3) anycombination thereof.

It can be noted that, in the absence of other controls (e.g., adding orremoving first heat exchange medium into the first heat exchange mediumcirculation loop as described herein, among other controls), decreasingthe second level of liquid phase of the first heat exchange medium inthe second heat exchanger 211 (or on the second heat exchange surfacefirst side 213) increases the first level of liquid phase of the firstheat exchange medium in the first heat exchanger (or on the first heatexchange surface second side 114) while increasing the second level ofliquid phase of the first heat exchange medium in the second heatexchanger 211 (or on the second heat exchange surface first side 213)decreases the first level of liquid phase of the first heat exchangemedium in the first heat exchanger (or on the first heat exchangesurface second side 114). Similarly, in the absence of other controls(e.g., adding or removing first heat exchange medium into the first heatexchange medium circulation loop as described herein, among othercontrols), decreasing the second level of liquid phase of the first heatexchange medium in the second heat exchanger 211 (or on the second heatexchange surface first side 213) decreases the pressure on the firstheat exchange surface second side 114 (and/or second heat exchangesurface first side 213, and/or first heat exchange medium) while theincreasing the second level of liquid phase of the first heat exchangemedium in the second heat exchanger 211 (or on the second heat exchangesurface first side 213) increases the pressure on the first heatexchange surface second side 114 (and/or second heat exchange surfacefirst side 213, and/or first heat exchange medium). Thus, controlmechanisms which control the first level of liquid phase of the firstheat exchange medium in the first heat exchanger (or on the first heatexchange surface second side 114) and/or the second level of liquidphase of the first heat exchange medium in the second heat exchanger 211(or on the second heat exchange surface first side 213) can also beutilized to control the pressure on the first heat exchange surfacesecond side 114 (and/or second heat exchange surface first side 213,and/or first heat exchange medium).

The heat exchange system 310 can also include a flow indicator 360located on or fluidly connected to the process line 201. The flowindicator 360 can include a flow meter and a display that indicates theflow rate of the first heat exchange medium that is measured by the flowmeter in process line 201. In an aspect, the measurements from flowindicator 360 in combination with other measurements, (e.g., first heatexchange medium temperatures measurements reported by temperatureindicators and/or controllers located on the first heat exchange mediumcirculation loop) can be utilized to determine how much heat isgenerated by the reaction mixture and/or determine the amount ofethylene reacted (i.e., ethylene conversion) in the reaction zone. Theflow meter can be any flow meter suitable for measuring a liquid phaseflow in a process line. In some aspects, the flow indicator 360 can beused i) to determine the amount of heat generated within the reactionzone 101, ii) to calculate the ethylene conversion within the reactionzone, iii) to control the reaction rate of the reaction in the reactionzone 101, or iv) combinations thereof. In a not shown aspect, the flowindicator can be 1) utilized to determine the amount of heat generated(e.g., through a calculation/processing unit coupled physically, viawire, or wirelessly to the flow indicator) within the reaction zoneand/or the ethylene conversation, and/or 2) coupled (physically, viawire, or wirelessly) to process equipment and/or logic control toactuate one or more control valve(s) (not shown) to control the flowrates of the one or more reaction mixture components (e.g., ethylene,catalyst system or catalyst system components, optionally organicreaction medium, optionally hydrogen, or combinations thereof) into thereaction mixture via the one or more reaction zone inlets.

Similar to heat exchange system 210 of FIG. 2 , heat exchange system 310of FIG. 3 includes a pressure controller 130 (with or without theoptional non-shown pressure sensor) and a pressure control device 131 influid communication with at least one of the process lines 201 (notshown) and/or 202 (shown) and process line 107 that is fluidly connectedto process line 201 by process line 107. As described for FIG. 2 , thepressure controllers of FIG. 3 can have the same features (e.g., outletline 109, non-shown pressure sensor, non-shown control valve, amongothers) and functions as described for FIG. 2 . For example, as in FIG.2 , pressure controller 130 and process line 107 in combination withoutlet line 109, the unshown pressure sensor, and/or the unshown controlvalve can be configured, and/or actuate devices, to 1) provide theinitial pressure (and/or in some instances control the pressure) on thefirst heat exchange surface second side 114 (or on second heat exchangesurface first side 213 or on the heat exchange medium), 2) to removenon-condensable components within the first heat exchange medium, or 3)any combination thereof. Generally, pressure control device 130 andpressure controller 131 and any ancillary equipment (e.g., process line107, the unshown pressure sensor, among other equipment) can beconfigured, can actuate devices, and/or can provide or control thepressure to be any pressure less than 1 atmosphere (101.3 kPa) describedherein on the first heat exchange surface second side 114 (or the secondheat exchange surface first side 213 and/or first heat exchange medium).

The heat exchange system 310 can further comprise temperature indicatorand/or controller 324. Temperature indicator 324 can be fluidlyconnected to, or located in, at least one of the plurality of conduitsallowing for flow of the first heat exchange medium from the first heatexchanger 111 (or from the first heat exchange surface second side 114)to the second heat exchanger 211 (or the second heat exchange surfacefirst side 213), e.g., process line 202, and is configured to measureand/or monitor the temperature of the first heat exchange medium. Insome aspects where vapor phase of the first heat exchange medium ispresent in the at least one of the plurality of conduits allowing forflow of the vapor phase of the first heat exchange medium from the firstheat exchange surface second side 114 to the second heat exchangesurface first side 213, temperature indicator and/or controller 334 inconjunction with a device and process logic to convert the temperaturereading to pressure can serve as a pressure sensor for at least one ofthe one or more pressure controllers described herein (e.g., pressurecontroller 131). In one aspect, temperature indicator and/or controller324 can be coupled to, or integrated into, at least one of the one ormore pressure controllers described herein (e.g., pressure controller131) and be utilized as the optional pressure sensor for at least one ofthe one or more pressure controllers described herein (e.g., pressurecontroller 131). In another aspect, temperature indicator and/orcontroller can be coupled (physically, via wire, or wirelessly) to atleast one of the one or more pressure controllers described herein(e.g., pressure controller 131). In an aspect, a temperature indicatorand/or controller 324, or temperature indicator and/or controller 324via at least one of the one or more pressure controllers (e.g., pressurecontroller 131), can be configured to actuate liquid control valve 308to control the second level of liquid phase first heat exchange mediumon the second heat exchange surface first side 213 (and/or the firstlevel of the first heat exchange medium on the first heat exchangesurface second side 114) in response to the temperature and/or pressuretransmitter to at least one of the one or more pressure control devices(e.g., pressure controller 131).

Reaction system 300 of FIG. 3 can further differ from reaction system200 of FIG. 2 by having a temperature indicator and/or controller 321 ina process line of the reaction zone 101 comprising the reaction mixture(also referred to herein as a reaction mixture process line).Temperature indicator and/or controller 321 can be fluidly connected to,or located within, a reaction mixture process line (e.g., process line103 (shown) or process line 102 (not shown)). While FIG. 3 showstemperature indicator and/or controller 321 as a single device,temperature indicator and/or controller 321 can comprise multipletemperature indicators and/or controllers located throughout thereaction zone process lines (including the reaction zone side of theheat exchange system, e.g., first heat exchanger or reaction zone sideof the first heat exchange surface first side 113). The multipletemperature indicators and/or controllers can be utilized eitherindividually or in combination (using control logic) to provide thefunction of temperature controller 321 (e.g., providing an averagereaction mixture temperature). Temperature controller and/or indicator321 can be configured to measure, monitor, and/or control a reactionmixture temperature (or average reaction mixture temperature) within thereaction zone.

Temperature indicator and/or controller 321 can be coupled with liquidcontrol valve 308; alternatively, coupled with at least one of the oneor more pressure control devices (e.g., pressure controller 130 and/or131); alternatively, liquid control valve 308 and at least one of theone or more pressure control devices (e.g., pressure controller 130and/or 131); or alternatively, liquid control valve 308 through at leastone of the one or more pressure control devices (e.g., pressurecontroller 130 and/or 131). In an aspect, temperature indicator and/orcontroller 321 can be configured to actuate liquid control valve 308 tocontrol the first level of the liquid phase of the first heat exchangemedium in the first heat exchanger 111 (or on the first heat exchangesurface second side 114) and/or the second level of the liquid phase ofthe first heat exchange medium in the second heat exchanger 211 (or onthe second heat exchange surface first side 213) in response to thereaction mixture temperature (or average reaction mixture temperature).In another aspect, temperature indicator and/or controller 321 can beconfigured to control a pressure set point of at least one of the one ormore pressure control devices (e.g., pressure controller 130 and/or 131)in response to reaction mixture temperature (or average reaction mixturetemperature). The temperature indicator and/or controller can be coupledto a control valve (not shown), the one or more pressure controldevices, or at least one of the one or more pressure control devices(e.g., pressure controller 130 and/or 131). Further, the temperatureindicator and/or controller 321 can be configured to actuate the controlvalve (not shown) to control the pressure on the first heat exchangesurface second side 114 and/or second heat exchange surface first side213 (or first heat exchange medium) in response to the reaction mixturetemperature (or average reaction mixture temperature). In anotheraspect, the temperature indicator and/or controller 321 is a) coupled toat least one of the pressure control devices (e.g. pressure controldevices 130 and/or 131 and configured to actuate a control valve (notshown) control a pressure set point of the one or more pressure controldevices in response to reaction mixture temperature (or average reactionmixture temperature)); b) coupled to the liquid control valve 308 andconfigured to actuate liquid control valve 308 to i) control the firstlevel of the liquid phase of the first heat exchange medium on the firstheat exchange surface second side (114), ii) control the second level ofthe liquid phase of the first heat exchange medium on the second heatexchange surface first side 213, or iii) any combination thereof; c)coupled with the first level indicator or controller 140 and configuredto i) actuate the first control valve 302 to allow the addition of firstheat exchange medium to the heat exchange system (or the first heatexchange medium circulation loop), and/or ii) actuate the second controlvalve 306 to allow the removal of first heat exchange medium from theheat exchange system (or the first heat exchange medium circulationloop) in response to reaction mixture temperature (or average reactionmixture temperature); or d) a combination thereof.

In an aspect, pressure controller 131 (with or without non-shownoptional pressure sensor), temperature controller 321, temperatureindicator 324 (which may or may not operate as the optional pressuresensor of pressure controller 131), at least one of the one or morepressure control devices (e.g., pressure control devices 130 and/or 131)and liquid control valve 308 can work together to control a) thereaction mixture temperature (or average reaction mixture temperature),b) the pressure on the first heat exchange surface second side 114 (orsecond heat exchange surface first side 213 or first heat exchangemedium), and/or c) the first level of the first heat exchange medium onthe first heat exchange surface second side 114 (and/or the second levelof the first heat exchange medium on the second heat exchange surfacefirst side 213). In an aspect, temperature indicator 134 in conjunctionwith a device and process logic to convert the temperature reading topressure can serve as a pressure sensor for pressure controller 131. Inan aspect, at least one of the one or more pressure controllers (e.g.,pressure controller 131) and/or a temperature controller (e.g.,temperature controller 321) can be configured to actuate a liquidcontrol valve (e.g., liquid control valve 308) to control the secondlevel of liquid phase first heat exchange medium on the second heatexchange surface first side 213 (and/or the first level of the firstheat exchange medium on the first heat exchange surface second side 114)in response to the pressure measured by at least one of the one or morepressure control devices (e.g., pressure controller 131) and/or thereaction mixture temperature measured by the temperature controller(e.g., temperature controller 321). In an aspect, pressure controldevice 131 can be a pressure controller having a pressure sensor (notshown) in process line 202 (or utilize the reading from temperatureindicator 324) and, optionally in conjunction with temperaturecontroller 321, can be configured to: 1) receive pressure measurementsignals from the pressure sensor (or converted temperature reading fromtemperature indicator 324), 2) optionally receive temperaturemeasurement signals from temperature sensor 321, and 3) perform controllogic to actuate control valve 308 (e.g., a liquid control valve) tocontrol (maintain, adjust, increase and/or decrease) the second level ofthe first heat exchange medium on the second heat exchange surface firstside 213 (and/or the first level of the first heat exchange medium onthe first heat exchange surface second side 114). In some aspects,pressure controller can perform control logic that causes pressurecontrol device 130 to control the pressure on the first heat exchangesurface second side 114 (or second heat exchange surface first side 213,or first heat exchange medium) and/or remove non-condensable componentsin the first heat exchange medium out of the heat exchange medium viaprocess lines 107 and 109.

In aspects, the components of reaction system 300 can work together tocontrol the reaction mixture temperature (or average reaction mixturetemperature by performing at least one or more of: a) controlling thepressure on the first heat exchange surface second side (or second heatexchange surface first side 213 and/or first heat exchange medium), b)controlling a first level of liquid phase of the first heat exchangemedium on the first heat exchange surface second side 114 (and/or asecond level of the first heat exchange medium on the second heatexchange surface first side 213), c) adding first heat exchange medium(liquid or vapor phase) to the heat exchange system 310 or removing aportion of the first heat exchange medium (liquid or vapor phase) fromthe heat exchange system 310; or d) controlling a flow of the first heatexchange medium out of the second heat exchanger 211 via liquid controlvalve 308.

In aspects, the components of reaction system 300 can work together tocontrol a pressure on the first heat exchange surface second side 114(or second heat exchange surface first side 213 or the first heatexchange medium) in the heat exchange system 310 by performing at leastone or more of: a) utilizing a pressure control device to provide and/orcontrol the pressure on the first heat exchange surface second side 114(or second heat exchange surface first side 213 or the first heatexchange medium), b) controlling a first level of first heat exchangemedium on the first heat exchange surface second side 114 (and/or asecond level of first heat exchange medium on the second heat exchangesurface first side 213, c) adding first heat exchange medium (liquid orvapor phase) to the heat exchange system 310 or removing a portion ofthe first heat exchange medium (liquid or vapor phase) from the heatexchange system 310, and d) controlling a flow of the first heatexchange medium out of the second heat exchanger 211 via liquid controlvalve 308.

As discussed herein, temperature controller 321, pressure controller 131(in conjunction with a control valve (not shown) and/or temperatureindicator and/or controller 324), liquid control valve 308, and/or levelcontroller 140 (in conjunction with inlet line 301 and outlet line 305and with their respective control values 302 and 306) can interactand/or can be integrated to control the reaction mixture temperature (oraverage reaction mixture temperature). For example, any combination,of 1) maintaining, increasing, or decreasing the second level of liquidphase of the first heat exchange medium in the second heat exchanger 211(or on the second heat exchange surface first side 213) by controllingliquid control valve 308 to control the flow rate of liquid phase of thefirst heat exchange medium out of the second heat exchange 211, 2)maintaining, increasing, or decreasing the pressure set point on (ormaintaining, increasing, or decreasing the pressure via) at least one ofthe one or more pressure controller devices (e.g., pressure controldevices 130 and/or 131), and/or 3) maintaining, increasing, ordecreasing the first level of liquid phase of the first heat exchangemedium in the first heat exchanger Ill (or on the first heat exchangesurface second side 114) by controlling the amount of first heatexchange medium in the first heat exchange medium circulation loop viaaction by level controller 140 to open control valve 302 or removing aportion of first heat exchange medium from the first heat exchangemedium circulation loop via action of level controller 140 on firstcontrol valve 306 and/or second control valve can be utilized to achievethe desired control of the reaction mixture temperature (averagereaction mixture temperature). It should be noted that when two or moreof the interactive and/or integrated controls are utilized to achieve adesired control in the reaction mixture temperature (or the averagereaction mixture temperature), not all of the interactive and/orintegrated controls must have the same effect on reaction mixturetemperature (average reaction mixture temperature) control as long asthe desired control in the reaction mixture temperature (averagereaction mixture temperature) is achieved. In these situations, othercontrols of the reaction system and/or heat exchange system may requireadjustment (increase or decrease) to maintain proper operation of thereaction system and/or heat exchange system. For example, 1) maintenanceof the reaction mixture temperature (average reaction mixturetemperature) can be achieved by an appropriate adjustment (increase ordecrease) of at least one of the control mechanisms that would result inan increase of the reaction mixture temperature (average reactionmixture temperature) and an appropriate adjustment (increase ordecrease) of at least one of the control mechanisms that would result inan equal decrease of the reaction mixture temperature (average reactionmixture temperature), 2) increasing the reaction mixture temperature(average reaction mixture temperature) can be achieved by an adjustment(increase or decrease) of at least one of the control mechanisms thatwould result in an increase of the reaction mixture temperature (averagereaction mixture temperature) and an adjustment (increase or decrease)of at least one of the control mechanisms that would result in a lessordecrease in the reaction mixture temperature (average reaction mixturetemperature), and 3) decreasing the reaction mixture temperature(average reaction mixture temperature) can be achieved by an adjustment(increase or decrease) of at least one of the control mechanism thatwould result in an decrease of the reaction mixture temperature (averagereaction mixture temperature) and an adjustment (increase or decrease)of at least one of the control mechanism that would result in a lessorincrease of the reaction mixture temperature (average reaction mixturetemperature), among other possibilities.

As discussed herein, pressure controller 131 (in conjunction with acontrol valve (not shown) and or temperature indicator and/or controller324), liquid control valve 308, and/or level controller 140 (inconjunction with inlet line 301 and outlet line 305 and with theirrespective control values 302 and 306) can interact and/or can beintegrated to control (maintain, adjust, increase or decrease) thepressure on the first heat exchange surface second 114 and/or the secondheat exchange surface first side 213 (or the first heat exchangemedium). For example, any combination, of 1) maintaining, increasing, ordecreasing the second level of liquid phase of the first heat exchangemedium in the second heat exchanger 211 (or on the second heat exchangesurface first side 213) by controlling liquid control valve 308 tocontrol the flow rate of liquid phase of the first heat exchange mediumout of the second heat exchange 211, 2) maintaining, increasing, ordecreasing the pressure set point on (or maintaining, increasing, ordecreasing the pressure via) at least one of the one or more pressurecontroller devices (e.g., pressure control devices 130 and/or 131),and/or 3) maintaining, increasing, or decreasing the first level ofliquid phase of the first heat exchange medium in the first heatexchanger 111 (or on the first heat exchange surface second side 114) bycontrolling the amount of first heat exchange medium in the first heatexchange medium circulation loop via action of level controller 140 onfirst control valve 302 and/or second control valve can be utilized toachieve the desired control (maintenance, adjustment, increase ordecrease) of the pressure on the first heat exchange surface second side114 and/or the second heat exchange surface first side 213 (or the firstheat exchange medium). It should be noted that when two or more of theinteractive and/or integrated controls are utilized to achieve a desiredcontrol of the pressure on the first heat exchange surface second side114 and/or the second heat exchange surface first side 213 (or the firstheat exchange medium), not all of the interactive and/or integratedcontrols must have the same effect on the pressure on the first heatexchange surface second side 114 and/or the second heat exchange surfacefirst side 213 (or the first heat exchange medium) control as long asthe desired control of the pressure on the first heat exchange surfacesecond side 114 and/or the second heat exchange surface first side 213(or the first heat exchange medium) is achieved. In these situations,other controls of the reaction system and/or heat exchange system mayrequire adjustment (increase or decrease) to maintain proper operationof the reaction system and/or heat exchange system. For example, 1)maintenance of the pressure on the first heat exchange surface secondside 114 and/or the second heat exchange surface first side 213 (or thefirst heat exchange medium) can be achieved by an appropriate adjustment(increase or decrease) of at least one of the control mechanisms thatwould result in an increase of the pressure and an appropriateadjustment (increase or decrease) of at least one of the controlmechanisms that would result in an equal decrease of the pressure on thefirst heat exchange surface second side 114 and/or the second heatexchange surface first side 213 (or the first heat exchange medium), 2)increasing the pressure on the first heat exchange surface second side114 and/or the second heat exchange surface first side 213 (or the firstheat exchange medium) can be achieved by an adjustment (increase ordecrease) of at least one of the control mechanisms that would result inan increase of the pressure and an adjustment of at least one of thecontrol mechanisms that would result in a lessor decrease in thepressure on the first heat exchange surface second side 114 and/or thesecond heat exchange surface first side 213 (or the first heat exchangemedium), and 3) decreasing the pressure on the first heat exchangesurface second side 114 and/or the second heat exchange surface firstside 213 (or the first heat exchange medium) can be achieved by anadjustment (increase or decrease) of at least one of the controlmechanism that would result in an decrease of the pressure and anadjustment (increase or decrease) of at least one of the controlmechanism that would result in a lessor increase of the pressure on thefirst heat exchange surface second side 114 and/or the second heatexchange surface first side 213 (or the first heat exchange medium),among other possibilities.

Generally, pressure control device 130 can be any pressure controldevice capable of providing less than 1 atmosphere (101.3 kPa) describedherein. FIG. 4 illustrates a non-limiting example of the pressurecontrol device 130 of FIG. 1 , FIG. 2 , and/or FIG. 3 . Pressure controldevice 130 can be embodied as a control valve 401 (e.g., a motive fluidcontrol valve) and an eductor 402. The motive fluid control valve 401can be connected to the pressure controller 131 of FIG. 1 , FIG. 2 ,and/or FIG. 3 and can be configured to actuate between a closed positionand an open position so as to disallow or allow a motive fluid (e.g.,steam or liquid water) in line 403 to flow into the eductor 402. Theeductor 402 is fluidly connected to the motive fluid line 403 via amotive fluid inlet 402 a. Eductor 402 is fluidly connected to the firstheat exchange fluid process line (e.g. first heat exchange mediumprocess line 202) via line 301 and eductor suction inlet 402 b. Thefirst heat exchange medium and/or non-condensable components in thefirst heat exchange medium process line 202 (or first heat exchangemedium circulation loop) exit the eductor (and the heat exchange system)along with the motive fluid via outlet line 309 through eductor outlet402 c. When the control valve 401 is actuated to an open position,motive fluid flows in line 403 to the eductor 402, and the flow ofmotive fluid through the eductor 402 creates a suction or vacuum on line301, which removes the first heat exchange medium and/or non-condensablecomponents in first heat exchange medium process line 202 (or the firstheat exchange medium circulation loop) from the heat exchange system.The first heat exchange medium, and/or non-condensable components infirst heat exchange medium process line 202 (or the first heat exchangemedium circulation loop) can flow from process line 202, into theeductor 402 via line 301 and out of the eductor 402 along with themotive fluid in line 309. When operating the heat exchange system suchthat a pressure on the heat exchange surface second side 114 (and/orsecond heat exchange surface first side 213 and/or heat exchange mediumdepending upon the actual heat exchange system) is any pressure lessthan 1 atmosphere (101.3 kPa) as disclosed herein, the suction or vacuumprovided by the eductor 402 to the heat exchange surface second side 114(and/or second heat exchange surface first side 213 and/or heat exchangemedium depending upon the actual heat exchange system) is a pressurethat is lower than the pressure on the heat exchange surface second side114 (and/or second heat exchange surface first side 213 and/or heatexchange medium depending upon the actual heat exchange system). In someaspects, it is contemplated that the pressure on the heat exchangesurface second side 114 (and/or second heat exchange surface first side213 and/or heat exchange medium depending upon the actual heat exchangesystem) can be provided and/or controlled to be any pressure less than 1atmosphere (101.3 kPa) using eductor 402 (e.g., in the heat exchangesystem 110 of reaction system 100); alternatively, eductor 402 can beutilized to provide the initial pressure in the heat exchange systemand/or remove non-condensable components in first heat exchange mediumprocess line 202 (e.g., in heat exchange system 210 of reaction system200 or heat exchange system 310 of reaction system 300).

FIG. 5 illustrates the pressure control device of FIG. 1 , FIG. 2 ,and/or FIG. 3 embodied as the control valve 401. Control valve 401 canbe connected to, via process line 109, a vacuum system (not shown) orvacuum supplying device (not shown). The control valve 401 can beconnected to the pressure controller 131 (and/or temperature controller321 in the case of heat exchange system 310 of reaction system 300) andbe configured to actuate between a closed position and an open position(upon receiving signals from the pressure controller 131) so as todisallow or allow the flow of first heat exchange medium and/ornon-condensable components in first heat exchange medium process line202 (or the first heat exchange medium circulation loop) from the heatexchange system. The pressure controller 131 (and/or temperaturecontroller 321 in the case of heat exchange system 310 of reactionsystem 300) can be configured to open the control valve 401 when apressure on the heat exchange surface first side 113 (in heat exchangesystem 210 of reaction system 200 or heat exchange system 310 ofreaction system 300) of the first heat exchange medium is greater thanthe desired pressure that is any pressure less than 1 atmosphere (101.3kPa) as described herein to i) provide an initial pressure on the heatexchange surface second side 114 (and/or the second heat exchangesurface first side 213 and/or first heat exchange medium depending uponthe actual heat exchange system), ii) control the pressure to anypressure less than any pressure less than 1 atmosphere (101.3 kPa) asdescribed herein on the heat exchange surface first side 113 (and/or thesecond heat exchange surface first side 213 and/or first heat exchangemedium depending upon the actual heat exchange system), and/or iii)remove non-condensable components in the first heat exchange medium. Inan aspect, control valve 401 (along with the non-shown vacuum system orvacuum suppling device) can replace or be utilized in conjunction witheductor 402 as described herein.

Reaction systems 100, 200, and 300 of FIG. 1 , FIG. 2 , and FIG. 3 ,respectively, can further comprise one or more reaction zone inlets (notshown) to introduce one or more reaction mixture components into thereaction zone. The reaction mixture components can comprise at leastethylene, a catalyst system or catalyst system components, optionally anorganic reaction medium, and optionally hydrogen. Reaction systems 100,200, and 300 of FIG. 1 , FIG. 2 , and FIG. 3 , respectively, can alsofurther comprise one or more reaction zone outlets (not shown) to removereaction mixture from the reaction zone. Reaction mixture removed fromthe reaction zone can be referred to as a reaction zone effluent. Thereaction zone effluent can comprise at least ethylene, catalyst system(or its components), oligomer product, optionally reaction medium, andoptionally hydrogen.

The reaction zone passing through heat exchange systems 110, 210 and 310of reaction systems 100, 200, and 300 (respectively) can be any reactionzone 101 where heat can be exchanged between a reaction mixture withinreaction zone 101 on the heat exchange surface first side 113 and thefirst heat exchange medium on the first heat exchange surface secondside 114. In an aspect, the reaction zone 101 can be one where thereaction mixture can make a single pass through the first heat exchangerIll (herein referred to as a single pass reaction zone or as a singlepass heat exchange system), or the reaction zone can be one where thereaction mixture can make several passes through the heat exchanger 111(herein referred to as a recycle reaction zone or a recycle heatexchange system). In an aspect, the reaction zone can be a single passreaction zone; or alternatively, a recycle reaction zone. It should benoted that the single pass reaction zone or single pass heat exchangesystem referred to herein should not be confused with single, 2-pass,3-pass, 4-pass, multipass, etc., heat exchangers where a fluid (e.g., areaction mixture) makes one or multiple passes through a single heatexchanger before finally exiting the heat exchanger (which can haveareas where the reaction mixture is not in contact the heat exchangesurface). The single pass reaction zone or single pass heat exchangesystem refers to a reaction zone or using a heat exchange system wherethe reaction mixture enters (or passes through) the heat exchange systema single time, exits the heat exchange system, and is then processed toisolate the desired product (e.g., oligomer product). The recyclereaction zone or recycle heat exchange system refers to a reaction zonehaving a circulation loop where the reaction mixture is circulatedthrough the heat exchange system multiple times prior to all of thereaction mixture being removed from the reaction zone (e.g., used in abatch reaction) or a portion of the reaction mixture being continuouslyor intermittently being removed from the reaction zone (e.g., used in acontinuous reaction) to be processed to isolate the desired product(e.g., oligomer product).

Heat exchange systems 110, 210 and 310 of reaction systems 100, 200, and300 (respectively) can be utilized in conjunction with a variety ofreaction zones 101. Reaction system 100, 200, and 300 as depictedinclude process lines 102 and 103. Reaction systems 100, 200, and 300only show process line 102 entering the heat exchanger 111 and processline 103 exiting heat exchanger 111, and thus reaction systems 100, 200,and 300 may, in some aspects, only show a portion of the entire reactionzone 101. One having ordinary skill in the art would recognize that heatexchange systems 110, 210 and 310 of reaction systems 100, 200, and 300(respectively) can be utilized for any reaction zone operating at areaction zone temperature less than the normal boiling point (i.e.,boiling point at 1 atmosphere (101.3 kPa)) of a utilized first heatexchange medium. For brevity, only process line 102 entering and processline 103 exiting and heat exchanger 110 relating to the reaction zone101 of reaction systems 100, 200, and/or 300 are shown in FIGS. 1, 2,and 3 . Depending upon the specific reaction system, process lines 102and 103 can be part of the reaction zone 101; or alternatively, processlines 102 and/or process line 103 may not be part of the reaction zone;i.e. process line 102 can represent one or more reaction mixturecomponent feed lines which can introduce one or more reaction mixtures(e.g., at least ethylene, a catalyst system or catalyst systemcomponents, optionally an organic reaction medium, and optionallyhydrogen) to reaction zone 101 or into reaction zone 101 within heatexchanger 111 while process line 103 can represent a reaction zoneoutlet line which can remove/withdrawn reaction mixture from thereaction zone 101 (or the first heat exchanger 111) and/or reaction zone101 within heat exchanger 111.

In an aspect, reaction zone 101 of reaction systems 100, 200, and 300 ofFIG. 1 . FIG. 2 , and FIG. 3 minimally comprise the portion of the heatexchanger 111 through which the reaction mixture flows (and contacts thefirst heat exchange surface first side) and which has all the necessaryreaction components and reaction conditions such that the reaction canoccur at a desired rate. In an aspect, at least a portion of processline 102 and/or process line 103 can form part of the reaction zone ifall the necessary reaction components and reaction conditions arepresent such that the reaction can occur at a desired rate. In oneaspect, process line 102 can represent one or more reaction mixturecomponent feed lines which can introduce one or more reaction mixturecomponents into the first heat exchanger 111. The reaction mixturecomponents which can be introduced via the one or more reaction mixturecomponent feed lines represented by process line 102 can compriseethylene, catalyst system or catalyst system components, optionallyorganic reaction medium, optionally hydrogen, or combinations thereof.In a combinable aspect, process line 103 can represent the reaction zoneoutlet lines which remove the reaction mixture from the reaction zone(or the first heat exchanger 111). In an aspect, at least a portion ofprocess lines 102 and 103 can represent a portion of the reaction zoneif all the necessary reaction components and reaction conditions arepresent in process lines 102 and/or 103 such that the reaction can occurat a desired rate. In an aspect, heat exchanger 111 can be a typicalheat exchanger (e.g., one or more plug flow reactors set up as a heatexchanger). In other aspects heat exchanger 111 can be one or morereactors independently selected from autoclave reactor, stirred tankreactor, or a continuous stirred tank reactor (CSTR) having internalheat exchange coils and/or external heat exchange jackets.

In an aspect, reaction zone 101 of reaction systems 100, 200, and 300 ofFIG. 1 , FIG. 2 , and FIG. 3 (respectively) can comprise first heatexchanger 111 (i.e., the first heat exchange surface first side 112through which the reaction mixture flows) and two or more reaction zonelines (e.g., process lines 102 and 103) through which the reactionmixture flows. Generally, the two or more reaction zone lines cancomprise the reaction mixture. At least one of the two or more reactionzone lines is a reaction zone first heat exchanger inlet line(s) (e.g.,process line 102) coupled to one or more first heat exchanger inlets(not numbered) and configured to introduce the reaction mixture into thefirst heat exchanger 111. The reaction mixture entering the first heatexchanger 111 is thus contacted with the first heat exchange surfacefirst side 113. At least one of the two or more reaction zone lines is areaction zone first heat exchanger outlet line(s) (e.g., process line103) coupled to one or more first heat exchanger outlets (not numbered)and configured to remove reaction mixture from the first heat exchanger111. The reaction mixture exiting the first heat exchanger 111 via atleast one of the two or more reaction zone lines is a reaction zonefirst heat exchanger outlet line(s) (e.g., process line 103) is thusremoved from contacting the first heat exchange surface first side 113.FIG. 6 , illustrates an aspect of a portion of reaction systems 100,200, and 300 of FIG. 1 , FIG. 2 , and FIG. 3 (respectively), wherein thereaction mixture is circulated through a reaction mixture circulationloop comprising first heat exchanger 111 (i.e., the first heat exchangesurface first side 113 through which the reaction mixture flows) and twoor more reaction zone lines (e.g., process lines 102 and 103). Thereaction zone 101 portion of reaction systems 100, 200, and 300 differfrom the reaction systems 100, 200, and 300 in that the reaction zone101 can further comprise a motive device fluidly connecting the reactionzone first heat exchanger inlet line(s) and the reaction zone first heatexchanger outlet line(s) configured to form a reaction mixturecirculation loop, where the motive device is configured to circulate thereaction mixture through the reaction mixture circulation loop.

The motive device 120 of the reaction zone 101 of reaction systems 100,200, and 300 of FIG. 1 , FIG. 2 , and FIG. 3 (respectively) can be anydevice which can cause the reaction mixture to circulate through thereaction mixture circulation loop. In an aspect the motive device 120can be any type of pump which can circulate the reaction mixture (e.g.,an in-line axial flow pump with a pump impeller, among others) throughmotive device 120 via motive device line 121. In an aspect, the motivedevice, during operation, can provide turbulent flow for the reactionmixture circulating through the reaction mixture circulation loop or atleast through the portion of the circulation loop where the reactionmixture contacts the first heat exchange surface second side. Theimpeller can be driven by a motor or other motive force. In someaspects, insulation can be placed around process lines 102 and/or 103,or any other part of the reaction zone 101 (e.g., a vessel) that is/arenot part of the heat exchange system 110 to reduce reaction mixture heatloss in these sections of the reaction zone.

In an aspect, the reaction zone 101 of reaction systems 100, 200, and/or300 depicted in FIG. 6 can further comprise one or more reactors (notshown). Each reactor can be located within the reaction mixturecirculation loop. In an aspect, each reactor independently, can belocated upstream of the motive device (at a position on the intake sideof a pump) or downstream of the motive device (on the discharge side ofthe pump). Each reactor independently can be fluidly connected to thereaction zone first heat exchanger inlet line(s) (e.g., process line102), the reaction zone first heat exchanger outlet line(s) (e.g.,process line 103), and the first heat exchange surface first side 113.In an aspect, each reactor independently can be located between motivedevice 120 and first heat exchanger inlet (e.g., on process line 102) orbetween the first heat exchanger outlet (e.g., process line 103). Inaspects where one or more other reactors are included as part of thereaction zone 101, each of the one or more reactors independently can bean autoclave reactor, a stirred tank reactor, a continuous stirred tankreactor, a plug flow reactor, or any combination thereof; alternatively,a stirred tank reactor, alternatively, a continuous stirred tankreactor, or alternatively, a plug flow reactor. In an aspect, each ofthe one or more reactors included as part of the reaction zone 101independently can have or not have internal heat exchange coil(s) and/orexternal heat exchange jacket(s). In some aspects, where one or moreother reactors are included as part of the reaction zone 101, each ofthe one or more reactors can be an autoclave reactor, continuous stirredtank reactor, a gas phase reactor, a solution reactor, a tubularreactor, a bubble reactor, or any combination thereof; alternatively,autoclave reactor; alternatively, stirred tank reactor; alternatively, agas phase reactor; alternatively, a solution reactor; alternatively, atubular reactor; or alternatively, a bubble reactor. In someembodiments, the reaction zone can comprise different types of reactorsin combination, and in various arrangements. In an embodiment, where oneor more other reactors are included as part of the reaction zone 101,each of the one or more reactors can have a mechanical agitator to stirand/or create turbulent flow within the vessel; alternatively, in placeof, or in conjunction with the mechanical agitator the one or morereactors can have internal baffles, a gas sparger, or any combinationthereof. Each of the one or more reactors included as part of thereaction zone independently can be located within process line 102and/or process line 103. In another aspect, the reaction zone 101 ofreaction systems 100, 200, and/or 300 depicted in FIG. 6 may notcomprise an independent reactor.

The processes and reaction of reaction systems described herein can be abatch process or a continuous process; alternatively, a batch process;or alternatively, a continuous process. In a batch process, thecomponents of the reaction mixture (e.g., at least ethylene, a catalystsystem or catalyst system components, optionally an organic reactionmedium, and optionally hydrogen) are introduced into the reaction zonevia one or more reaction zone inlets (not shown) and reaction mixturecirculated through the reaction zone, thereby passing through the firstheat exchanger 111 of heat exchange systems 110, 210, or 310 to form thedesired product (e.g., an oligomer product). Generally, the reactionmixture is circulated through the reaction zone until a desiredfeedstock (e.g., ethylene) conversion is achieved, a desired catalystsystem productivity is achieved, and/or a desired quantity of product(e.g., oligomer product) is produced. In the continuous process, thecomponents of the reaction mixture (e.g., at least ethylene, a catalystsystem or catalyst system components, optionally an organic reactionmedium, and optionally hydrogen) are continuously or intermittentlyintroduced into the reaction zone via one or more reaction zone inlets(not shown) while reaction mixture is continuously or intermittentlywithdrawn from the reaction zone (alternatively a reaction zone effluentis withdrawn from the reaction zone). The continuous reaction zone isoperated to provide a desired feedstock (e.g., ethylene) conversion, adesired catalyst system productivity, and/or a desired product (e.g.,oligomer product) discharge rate.

The reaction systems described herein can be selected from the groupconsisting of an ethylene oligomerization reaction system, an ethylenetrimerization reaction system, an ethylene tetramerization reactionsystem, and an ethylene trimerization and tetramerization reactionsystem; alternatively, an ethylene oligomerization reaction system;alternatively, an ethylene trimerization reaction system; alternatively,an ethylene tetramerization reaction system; or alternatively, anethylene trimerization and tetramerization reaction system. Designs forreactor/reaction zone are described in U.S. Pat. No. 10,513,473 toKreischer, entitled “EthyleneOligomerization/Trimerization/Tetramerization Reactor”. The designsdescribed therein and the features of the processes, reactors, reactionzones, and/or reaction systems can be utilized to further describeprocesses, reactors, reaction zones, and/or reaction systems describedherein. In an aspect, of the processes and reaction systems describedherein, not all of the reaction mixture may contact the first heatexchange surface first side or indirectly contact the first heatexchange medium at the same time. Consequently, in an aspect, at least aportion of the reaction mixture can contact the first heat exchangesurface first side or can indirectly contact the first heat exchangemedium. Generally, the portion of the reaction mixture that contacts thefirst heat exchange surface first side or indirectly contacts the firstheat exchange medium is considered to be the volume of the reactionmixture included in the interior volume of the first heat exchangesurface. For example, for a cylindrical portion of the reaction zone,the at least a portion of the reaction mixture that contacts the firstheat exchange surface first side, or indirectly contacts the first heatexchange medium, is the portion of the reaction mixture within theinterior volume of the cylinder having theoretical end planes at thelocation between where the first heat exchange surface begins and ends.The portion of the reaction mixture that falls within the theoreticalend planes at the location between where the first heat exchange surfacebegins and ends can be referred to as the heat exchanged reactionmixture volume. In an aspect, a ratio of heat exchanged reaction mixturevolume to the total reaction mixture volume within the reaction zone canhave a minimum value of (i.e., or greater than or equal to) 1:1, 1.5:1,2:1, 2.5:1, 3:1, or 4:1; alternatively or additionally, a maximum valueof (i.e., less than or equal to) 100:1, 50:1, 20:1, 15:1, 12:1, or 9:1.In an aspect, the ratio of heat exchanged reaction mixture volume to thetotal reaction mixture volume within the reaction zone can range fromany minimum value disclosed herein to any maximum value disclosedherein. In some non-limiting aspects, the ratio of heat exchangedreaction mixture volume to the total reaction mixture volume within thereaction zone can range from 1:1 to 100:1, from 1.5:1 to 100:1, from 2:1to 100:1, from 3:1 to 100:1, from 4:1 to 100:1, from 3:1 to 50:1, from3:1 to 20:1, from 4:1 to 50:1, from 4:1 to 15:1, or from 4:1 to 12:1.Other ratios of heat exchanged reaction mixture volume to the totalreaction mixture volume within the reaction zone are readily apparent tothose skilled in the art with the aid of this disclosure.

The processes and reaction systems described herein can provideadvantageous temperature control. In an aspect, a temperature differencebetween an average reaction mixture temperature on the first heatexchange surface first side and a first heat exchange medium temperatureon the first heat exchange surface second side can be, or can becontrolled to be less than 20° C., 15° C., 10° C. 7.5° C., 5° C., 4° C.,or 3° C.; alternatively, or additionally, the first heat exchange mediumtemperature on the first heat exchange surface second side can be (orcan be controlled to be) within any percentage of an average reactionmixture temperature on the first heat exchange surface first sidedisclosed herein (e.g., 20%, 15%, 12.5%, 10%, 7.5%, 6%, 5%, or 4.5%). Inan aspect, a reaction mixture temperature at any point in the reactionzone can be, or can be controlled to be, within 15° C., 10° C., 7.5° C.,5° C., 4° C., 3° C., or 2° C. of an average reaction mixture temperaturein the reaction zone; alternatively or additionally, a reaction mixturetemperature at any point in the reaction zone can be, or can becontrolled to be, within 3%, 2%, 1.5%, 1%, 0.8%, 0.6%, 0.5%, 0.45%,0.4%, 0.35%, 0.3%, 0.25%, or 0.2% of an average reaction mixturetemperature in the reaction zone. The temperature percentage valuesrefer to a comparison of the temperatures on an absolute temperaturescale (i.e., K or ° R).

The reaction system can have a ratio of the heat exchanged reactionmixture volume to the total reaction mixture volume selected to maintaina desired temperature and/or temperature profile of the reaction mixturewithin the reaction zone. In an embodiment, the minimum ratio of theheat exchanged reaction mixture volume to the total reaction mixturevolume can be greater than or equal to 0.7, 0.75, or 0.8; alternativelyor additionally, the maximum ratio of the heat exchanged reactionmixture volume to the total reaction mixture volume can be less than orequal to 1.0, 0.975, 0.95, 0.925, or 0.9. In an embodiment, the ratio ofthe heat exchanged reaction mixture volume to the total reaction mixturevolume can range from any minimum the ratio of the heat exchangedreaction mixture volume to the total reaction mixture volume describedherein to any maximum the ratio of the heat exchanged reaction mixturevolume to the total reaction mixture volume described herein. In someembodiments, suitable ranges for the ratio of the heat exchangedreaction mixture volume to the total reaction mixture volume caninclude, but are not limited to, from 0.7 to 1.0, from 0.75 to 1, from0.8 to 1, from 0.75 to 0.975, from 0.75 to 0.95, from 0.8 to 0.975, from0.8 to 0.95, or from 0.8 to 0.925. Other suitable ranges for the ratioof the heat exchanged reaction mixture volume to the total reactionmixture volume are readily apparent from the present disclosure.

The process described herein can further comprise a) introducing atleast 1) ethylene, 2) a catalyst system or catalyst system componentscomprising i) a heteroatomic ligand transition metal compound complexand an organoaluminum compound or ii) a heteroatomic ligand, atransition metal compound, and an organoaluminum compound, 3)optionally, an organic reaction medium, and 4) optionally, hydrogen intoa reaction zone (or into a reaction mixture within a reaction zone); andb) forming an oligomer product in the reaction zone. For the reactionsystems described herein, at least 1) ethylene, 2) a catalyst system orcatalyst system components comprising i) a heteroatomic ligandtransition metal compound complex and an organoaluminum compound or ii)a heteroatomic ligand, a transition metal compound, and anorganoaluminum compound, 3) optionally, an organic reaction medium, and4) optionally, hydrogen can be introduced into the reaction zone (orinto the reaction mixture in the reaction zone). Generally, the reactionmixture of the process described herein and the reaction zone of thereaction systems described herein can comprise at least 1) ethylene, 2)a catalyst system or catalyst system components comprising i) aheteroatomic ligand transition metal compound complex and anorganoaluminum compound or ii) a heteroatomic ligand, a transition metalcompound, and an organoaluminum compound, 3) an oligomer product, 4)optionally, an organic reaction medium, and 5) optionally, hydrogen. Thecatalyst system, catalyst components, heteroatomic ligand transitionmetal compound complex, heteroatomic ligand, transition metal compound,organoaluminum compound, and optional organic reaction medium, areindependently described herein and these independent descriptions can beutilized without limitation and in any combination to further describethe processes and reactions systems described herein.

The processes and reaction systems disclosed herein can utilize acatalyst system or catalyst system components comprising i) aheteroatomic ligand transition metal compound complex and anorganoaluminum compound or ii) a heteroatomic ligand, a transition metalcompound, and an organoaluminum compound; alternatively, a heteroatomicligand transition metal compound complex and an organoaluminum compound;or alternatively, a heteroatomic ligand, a transition metal compound,and an organoaluminum compound. In some aspects, the catalyst system (orcatalyst system mixture) comprising i) a heteroatomic ligand transitionmetal compound complex and an organoaluminum compound or ii) aheteroatomic ligand, a transition metal compound, and an organoaluminumcompound) is introduced into the reaction mixture within the reactionzone. In other aspects, the two or more of catalyst system components(e.g., catalyst system components) comprising a heteroatomic ligandtransition metal compound complex and an organoaluminum compound or ii)a heteroatomic ligand, a transition metal compound, and anorganoaluminum compound) are separately introduced into the reactionmixture within the reaction zone. The heteroatomic ligand, theheteroatomic ligand of the heteroatomic ligand transition metal compoundcomplex, the transition metal compound, the transition metal compound ofthe heteroatomic ligand transition metal compound, the heteroatomicligand transition metal compound complex, and the organoaluminumcompound are independent elements of the catalyst system or catalystsystem components used in the processes described herein and areindependently described herein. These independently described catalystsystem or catalyst system component elements can be utilized in anycombination, and without limitation, to further describe the processesprovided herein.

In an aspect, the catalyst system or the catalyst system components cancomprise 1) a heteroatomic ligand and a transition metal compound or ii)a heteroatomic ligand transition metal compound complex; alternatively,a heteroatomic ligand and a transition metal compound; or alternatively,a heteroatomic ligand transition metal compound complex. Generally, theheteroatomic ligand transition metal compound complex of the catalystsystems described herein can be composed of the heteroatomic ligand andthe transition metal compound. The heteroatomic ligand and thetransition metal compound are independent elements of the heteroatomicligand transition metal compound complex and are independently describedherein. The independent descriptions of the heteroatomic ligand and thetransition metal compound can be utilized without limitation, and in anycombination, to further describe the catalyst system heteroatomic ligandtransition metal compound complex or the heteroatomic ligand andtransition metal compound of the catalyst systems described herein.

Generally, the heteroatomic ligand or the heteroatomic ligand of theheteroatomic ligand transition metal compound complex can be anyheteroatomic ligand, which when utilized in the catalysts systems (or asa component in the catalyst systems) described herein for the processesand/or reaction systems described herein, can form an oligomerproduction in the reaction zone. In an aspect, the heteroatomic ligandor the heteroatomic ligand of the heteroatomic ligand transition metalcompound complex can be a neutral heteroatomic ligand or an anionicheteroatomic ligand; alternatively, a neutral heteroatomic ligand; oralternatively, an anionic heteroatomic ligand. In an aspect, the neutralheteroatomic ligand can comprise one or more heteroatomic complexingmoieties; alternatively, two heteroatomic complexing; or alternatively,three heteroatomic complexing moieties. In an aspect, the anionicheteroatomic ligand can also comprise one or more neutral heteroatomiccomplexing moieties; alternatively, two heteroatomic complexing; oralternatively, three heteroatomic complexing moieties. In an aspect, theeach neutral heteroatomic complexing moiety of the neutral ligand or theanionic ligand comprising a neutral heteroatomic complexing moietyindependently can be an ether group, a sulfide group, an amine group, animine group, a phosphine group, a phosphinite group, a phosphonitegroup, or a phosphite group; alternatively, an ether group, a sulfidegroup, an amine group, an imine group, or a phosphine group;alternatively, an ether group; alternatively, a sulfide group;alternatively, an amine group; alternatively, an imine group; oralternatively, a phosphine group. In an aspect, the anion atom of theanionic heteroatomic ligand (which forms a covalent or ionic bond withthe transition metal of the transition metal compound) can be an anioniccarbon atom, an anionic oxygen atom, or an anion nitrogen atom;alternatively, an anionic carbon atom; alternatively, an anionic oxygenatom; or alternatively, an anion nitrogen atom.

In an aspect, the heteroatomic ligand transition metal compound complexcan have the general formula [(HetLig)MX_(p)Q_(q)]^(s-p); wherein HetLigrepresents the heteroatomic ligand, M represents the transition metal, Xis an monoanionic ligand and p is an integer, Q is a neutral ligand, qis an integer, s is an integer representing the oxidation state of thetransition metal M. and wherein any two or more of the X and Q ligandsmay be linked to form a multidentate ligand. Therefore, for the generaland specific structures disclosed hereinbelow, it is envisioned that anytwo or more of the X and Q ligands can form a chelating ligand in whicha bridging moiety links X ligands, Q ligands, or a combination of X andQ ligands. In an non-limiting aspect, the heteroatomic ligand-metalcompound complex can be heteroatomic ligand chromium compound complexand can have the general formula [(HetLig)CrX_(p)Q_(q)]^(s-p); whereinHetLig represents the one or more first training heteroatomic ligands, Xis an monoanionic ligand and p is an integer, Q is a neutral ligand, qis an integer, and s is an integer representing the oxidation state ofthe chromium atom, and wherein any two or more of the X and Q ligandsmay be linked to form a multidentate ligand. Therefore, for the generaland specific structures disclosed hereinbelow, it is envisioned that anytwo or more of the X and Q ligands can form a chelating ligand in whicha bridging moiety links X ligands, Q ligands, or a combination of X andQ ligands.

In any aspect, the heteroatomic ligand or the heteroatomic ligand of theheteroatomic ligand transition metal compound complex can comprise, canconsist essentially of, or can be, an N²-phosphinyl formamidine, anN²-phosphinyl amidine, an N²-phosphinyl guanidine, a heterocyclic2-[(phosphinyl)aminyl]imine, or any combination thereof; alternatively,an N²-phosphinyl formamidine; alternatively, an N²-phosphinyl amidine;alternatively, an N²-phosphinyl guanidine; or alternatively, aheterocyclic 2-[(phosphinyl)aminyl]imine. Generally, the anN²-phosphinyl formamidine can have Structure NPF1, the N²-phosphinylamidine can have Structure NPA1, the N²-phosphinyl guanidine can haveStructure Gu1, Structure Gu2, Structure Gu3, Structure Gu4, or StructureGu5, and the heterocyclic 2-[(phosphinyl)aminyl]imine can have structureHCPA1. In some aspects, the N²-phosphinyl guanidine have Structure Gu2,Structure Gu3, or Structure Gu4; alternatively, Structure Gu1;alternatively, Structure Gu2; alternatively, Structure Gu3;alternatively, Structure Gu4; or alternatively, Structure Gu5.

In any aspect, the heteroatomic ligand transition metal compound complexcan comprise, can consist essentially of, or can be, an N²-phosphinylformamidine transition metal compound complex, an N²-phosphinyl amidinetransition metal compound complex, an N²-phosphinyl guanidine transitionmetal compound complex, a heterocyclic 2-[(phosphinyl)aminyl]iminetransition metal compound complex, or any combination thereof;alternatively, an N²-phosphinyl formamidine transition metal compoundcomplex; alternatively, an N²-phosphinyl amidine transition metalcompound complex; alternatively, an N²-phosphinyl guanidine transitionmetal compound complex; alternatively, an N²-phosphinyl guanidinetransition metal compound complex; or alternatively, a heterocyclic2-[(phosphinyl)aminyl]imine transition metal compound complex.Generally, the an N²-phosphinyl formamidine transition metal compoundcomplex can have Structure NPFM1, the N²-phosphinyl amidine transitionmetal compound complex can have Structure NPAM1, the N²-phosphinylguanidine transition metal compound complex can have Structure GuM1,Structure GuM2, Structure GuM3, Structure GuM4, or Structure GuM5, andthe heterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplex can have Structure HCPAM1. In some aspects, the N²-phosphinylguanidine transition metal compound complex have Structure GuM2,Structure GuM3, or Structure GuM4; alternatively, Structure GuM1;alternatively, Structure GuM2; alternatively, Structure GuM3;alternatively, Structure GuM4; or alternatively, Structure GuM5.

Within the N²-phosphinyl formamidines, the N²-phosphinyl formamidinetransition metal compound complexes, the N²-phosphinyl amidines, theN²-phosphinyl amidine transition metal compound complexes, and theheterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplexes the nitrogen participating in a double bond with the centralcarbon atom is referred to as the N¹ nitrogen and the nitrogen atomparticipating in a single bond with the central carbon atom is referredto as the N² nitrogen. Similarly, within the N²-phosphinyl guanidinesand the N²-phosphinyl guanidine transition metal compound complexes, thenitrogen participating in a double bond with the central carbon atom ofthe guanidine core is referred to as the N¹ nitrogen, the nitrogen atomparticipating in a single bond with the central carbon atom of theguanidine core and a bond with the phosphorus atom of the phosphinylgroup is referred to as the N² nitrogen, and the remaining nitrogen atomparticipating in a single bond with the central carbon atom of theguanidine core is referred to as the N³ nitrogen. It should be notedthat the guanidine group of the guanidine in the N²-phosphinylguanidines and the N²-phosphinyl guanidine transition metal compoundcomplexes can be a portion of a larger group which does not containguanidine in it name. For example, while the compound7-dimethylphosphinylimidazo[1,2-a]imidazole could be classified as acompound having an imidazo[1,2-a]imidazole core (or a compound having aphosphinylimidazo[1,2-a]imidazole group),7-dimethylphosphinylimidazo[1,2-a]imidazole would still be classified asa compound having a guanidine core (or as a compound having an guanidinegroup) since it contains the defined general structure of the guanidinecompound.

The R¹, R³, R⁴, and R⁵ groups within the N²-phosphinyl formamidinestructures and the N²-phosphinyl formamidine transition metal compoundcomplex structures, R¹, R², R³, R⁴, and R⁵ within the N²-phosphinylamidine structures and the N²-phosphinyl amidine transition metalcompound complex structures, R¹, R^(2a), R^(2b), R³, R⁴, R⁵, L¹², L²²,and L²³ within the N²-phosphinyl guanidine structures and theN²-phosphinyl guanidine transition metal compound complex structures,and L¹², T, R³, R⁴, and R⁵ within the heterocyclic2-[(phosphinyl)aminyl]imine structures and heterocyclic2-[(phosphinyl)aminyl]imine transition metal compound complex structuresare independently described herein and can be utilized in anycombination and without limitation to further describe the N²-phosphinylformamidine structures, the N²-phosphinyl formamidine transition metalcompound complex structures, the N²-phosphinyl amidine structures, theN²-phosphinyl amidine transition metal compound complex structures, theN²-phosphinyl guanidine structures, the N²-phosphinyl guanidinetransition metal compound complex structures, the heterocyclic2-[(phosphinyl)aminyl]imine structures, and the heterocyclic2-[(phosphinyl)aminyl]imine transition metal compound complex structuresdisclosed herein. X_(p), Q, and q of the N²-phosphinyl formamidinetransition metal compound complex structures, the N²-phosphinyl amidinetransition metal compound complex structures, the N²-phosphinylguanidine transition metal compound complex structures, and theheterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplex structures are independently described herein and can beutilized in any combination, and without limitation, to further describethe N²-phosphinyl formamidine transition metal compound complexstructures, the N²-phosphinyl amidine transition metal compound complexstructures, the N²-phosphinyl guanidine transition metal compoundcomplex structures, and the heterocyclic 2-[(phosphinyl)aminyl]iminetransition metal compound complex structures disclosed herein.Additionally, the independent descriptions of X_(p), Q, and q can becombined, without limitation, with the independently described R¹, R²,R^(2a), R^(2b), R³, R⁴, R⁵, L¹², L²², and L²³ to further describe theappropriate N²-phosphinyl formamidine transition metal compound complexstructures, the N²-phosphinyl amidine transition metal compound complexstructures, the N²-phosphinyl guanidine transition metal compoundcomplex structures, and the heterocyclic 2-[(phosphinyl)aminyl]iminetransition metal compound complex structures contemplated herein.

Generally, R¹ of the N²-phosphinyl formamidines, the N²-phosphinylformamidine transition metal compound complexes, the N²-phosphinylamidines, the N²-phosphinyl amidine transition metal compound complexes,the N²-phosphinyl guanidines, and/or the N²-phosphinyl guanidinetransition metal compound complexes which have an R group can be anorganyl group; alternatively, an organyl group consisting of inertfunctional groups; or alternatively, a hydrocarbyl group. In an aspect,the R¹ organyl group can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or aC₁ to C₅ organyl group. In an aspect, the R¹ organyl group consisting ofinert functional groups can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, ora C₁ to C₅ organyl group consisting of inert functional groups. In anaspect, the R¹ hydrocarbyl group can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁to C₁₀, or a C₁ to C₅ hydrocarbyl group.

In an aspect, R¹ of the N²-phosphinyl formamidines, the N²-phosphinylformamidine transition metal compound complexes, the N²-phosphinylamidines, the N²-phosphinyl amidine transition metal compound complexes,the N²-phosphinyl guanidines, and/or the N²-phosphinyl guanidinetransition metal compound complexes which have an R group can be analkyl group, a substituted alkyl group, a cycloalkyl group, asubstituted cycloalkyl group, an aryl group, a substituted aryl group,an aralkyl group, or a substituted aralkyl group; alternatively an alkylgroup or a substituted alkyl group; alternatively, a cycloalkyl group ora substituted cycloalkyl group; alternatively, an aryl group or asubstituted aryl group; alternatively, an aralkyl group or a substitutedaralkyl group; alternatively, an alkyl group, a cycloalkyl group, anaryl group, or an aralkyl group; alternatively, an alkyl group;alternatively, a substituted alkyl group, alternatively, a cycloalkylgroup; alternatively, a substituted cycloalkyl group; alternatively, anaryl group; alternatively, a substituted aryl group; alternatively, anaralkyl group; or alternatively, a substituted aralkyl group. In anyaspect disclosed herein, the R¹ alkyl group can be a C₁ to C₂₀, a C₁ toC₁₀, or a C₁ to C₅ alkyl group. In any aspect disclosed herein, the R¹substituted alkyl group can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅substituted alkyl group. In any aspect disclosed herein, the R¹cycloalkyl group can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀cycloalkyl group. In any aspect disclosed herein, the R¹ substitutedcycloalkyl group can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀substituted cycloalkyl group. In any aspect disclosed herein, the R¹aryl group can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ aryl group.In any aspect disclosed herein, the R¹ substituted aryl group can be aC₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ substituted aryl group. In anyaspect disclosed herein, the R¹ aralkyl group can be a C₇ to C₂₀, a C₇to C₁₅, or a C₇ to C₁₀ aralkyl group. In any aspect disclosed herein,the R¹ substituted aralkyl group can be a C₇ to C₂₀, a C₇ to C₁₅, or aC₇ to C₁₀ substituted aralkyl group. Each substituent of a substitutedalkyl group (general or specific), a substituted cycloalkyl group(general or specific), a substituted aryl group (general or specific),and/or substituted aralkyl group (general or specific) can be a halogen,a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogenor a hydrocarbyl group; alternatively, a halogen or a hydrocarboxygroup; alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted R¹ group.

In an aspect, R¹ can be a methyl group, an ethyl group, a propyl group,a butyl group, a pentyl group, a hexyl group, a heptyl group, or anoctyl group; or alternatively, a methyl group, an ethyl group, an-propyl (1-propyl) group, an iso-propyl (2-propyl) group, a tert-butyl(2-methyl-2-propyl) group, or a neopentyl (2,2-dimethyl-1-propyl) group.In some aspects, the alkyl groups which can be utilized as R¹ can besubstituted. Each substituent of a substituted alkyl group (general orspecific) independently can be a halogen or a hydrocarboxy group;alternatively, a halogen; or alternatively, a hydrocarboxy group.Substituent halogens and substituent hydrocarboxy groups (general andspecific) are independently disclosed herein. These substituent halogensand substituent hydrocarboxy groups can be utilized without limitationto further describe a substituted alkyl group which can be utilized asR¹.

In an aspect, R¹ can be a cyclopentyl group, a substituted cyclopentylgroup, a cyclohexyl group, or a substituted cyclohexyl group;alternatively, a cyclopentyl group or a substituted cyclopentyl group;or alternatively, a cyclohexyl group or a substituted cyclohexyl group.In an aspect, the substituted cycloalkyl group, which can be utilized asR¹, can be a 2-substituted cyclohexyl group, a 2,6-disubstitutedcyclohexyl group, a 2-substituted cyclopentyl group, or a2,5-disubstituted cyclopentyl group; alternatively, a 2-substitutedcyclohexyl group or a 2,6-disubstituted cyclohexyl group; alternatively,a 2-substituted cyclopentyl group or a 2,5-disubstituted cyclopentylgroup; alternatively, a 2-substituted cyclohexyl group or a2-substituted cyclopentyl group; or alternatively, a 2,6-disubstitutedcyclohexyl group or a 2,5-disubstituted cyclopentyl group. In an aspect,one or more substituents of a multi-substituted cycloalkyl grouputilized as R¹ can be the same or different; alternatively, all thesubstituents of a multi-substituted cycloalkyl group can be the same, oralternatively, all the substituents of a multi-substituted cycloalkylgroup can be different. Each substituent of a substituted cycloalkylgroup having a specified number of ring carbon atoms independently canbe a halogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen, alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy (general and specific) groups are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups can be utilized withoutlimitation to further describe a substituted cycloalkyl group (generalor specific) which can be utilized as R¹.

In a non-limiting aspect, R¹ can be a cyclohexyl group, a2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group; oralternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describealkylcyclohexyl groups (general and specific), dialkylcyclohexyl groups(general and specific), alkylcyclopentyl groups (general or specific),and/or dialkylcyclopentyl groups (general and specific) which can beutilized as R¹. Generally, the alkyl substituents of a dialkylcyclohexylgroup or a dialkylcyclopentyl group can be the same; or alternatively,the alkyl substituents of a dialkylcyclohexyl group or adialkylcyclopentyl group can be different. In some non-limiting aspects,R¹ can be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group.In other non-limiting aspects, R¹ can be a 2-methylcyclohexyl group, a2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a2-tert-butylcyclohexyl group; or alternatively, a 2,6-dimethylcyclohexylgroup, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group,or a 2,6-di-tert-butylcyclohexyl group.

In an aspect, R¹ can be a phenyl group, a substituted phenyl group;alternatively, a phenyl group; or alternatively, a substituted phenylgroup. In an aspect, the substituted phenyl group, which can be utilizedas R¹, can be a 2-substituted phenyl group, a 3-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,or a 2,6-disubstituted phenyl group; alternatively, a 3-substitutedphenyl group or a 3,5-disubstituted phenyl group; alternatively, a2-substituted phenyl group or a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Inan aspect, one or more substituents of a multi-substituted phenyl grouputilized as R¹ can be the same or different, alternatively, all thesubstituents of a multi-substituted cycloalkyl group can be the same; oralternatively, all the substituents of a multi-substituted cycloalkylgroup different. Each substituent of a substituted phenyl group (generalor specific) independently can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a halogen or a hydrocarboxy group; alternatively, ahydrocarbyl group or a hydrocarboxy group; alternatively, a halogen,alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently disclosed herein. These substituent halogens,substituent hydrocarbyl groups, and substituent hydrocarboxy groups canbe utilized without limitation to further describe a substituted phenylgroup (general or specific) which can be utilized as R¹.

In a non-limiting aspect, R¹ can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenyl groupor a 2,6-dialkylphenyl group; alternatively, a 3-alkylphenyl group or a3,5-dialkylphenyl group; alternatively, a 2-alkylphenyl group or a2,6-dialkylphenyl group; or alternatively, a 2,4,6-trialkylphenyl group.Alkyl substituent groups (general and specific) are independentlydescribed herein and these alkyl substituent groups can be utilized,without limitation, to further describe any alkyl substituted phenylgroup which can be utilized as R¹. Generally, the alkyl substituents ofa dialkylphenyl group (general or specific) or a trialkylphenyl group(general or specific) can be the same; or alternatively, the alkylsubstituents of a dialkylphenyl group or trialkylphenyl group can bedifferent. In some non-limiting aspects, R¹ independently can be aphenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a2-n-propylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, a phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, aphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group.

In an aspect, R¹ can be a benzyl group or a substituted benzyl group;alternatively, a benzyl group; or alternatively, a substituted benzylgroup. Each substituent of a substituted benzyl group independently canbe a halogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, a halogen or a hydrocarbyl group: alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen, alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy groups (general and specific) are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups can be utilized withoutlimitation to further describe a substituted benzyl group (general orspecific) which can be utilized as R¹.

Generally, R² of the N²-phosphinyl amidines and/or the N²-phosphinylamidine transition metal compound complexes can be an organyl group;alternatively, an organyl group consisting of inert functional groups;or alternatively, a hydrocarbyl group. In an aspect, the R² organylgroup can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅organyl group. In an aspect, R² organyl group consisting of inertfunctional groups can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁to C₅ organyl group consisting of inert functional groups. In an aspect,R² hydrocarbyl group can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or aC₁ to C₅ hydrocarbyl group.

In an aspect, R² of the N²-phosphinyl amidines and/or the N²-phosphinylamidine transition metal compound complexes can be an acyl group or asubstituted acyl group; an acyl group; or alternatively, a substitutedacyl group. In an aspect, the acyl group can be a C₁ to C₂₀, a C₁ toC₁₅, a C₁ to C₁₀, or a C₁ to C₅ acyl group. In an aspect, thesubstituted acyl group can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, ora C₁ to C₅ a substituted acyl group. In some aspects, R² of theN²-phosphinyl amidines and/or the N²-phosphinyl amidine transition metalcompound complexes can be an alkanoyl group, a substituted alkanoylgroup, a benzoyl group, or a substituted benzoyl group; alternatively,an alkanoyl group or a substituted alkanoyl group; alternatively, abenzoyl group, or a substituted benzoyl group; alternatively, analkanoyl group; alternatively, a substituted alkanoyl group;alternatively, a benzoyl group; or alternatively, a substituted benzoylgroup. In any aspect disclosed herein, the R² alkanoyl group can be a C₁to C₂₀, a C₁ to C₁₀, or a C₁ to C₅ alkanoyl group. In any aspectdisclosed herein, the R² substituted alkanoyl group can be a C₁ to C₂₀,a C₁ to C₁₀, or a C₁ to C₅ substituted R² alkanoyl group. In any aspectdisclosed herein, the R² benzoyl group can be a C₇ to C₂₀, a C₇ to C₁₅,or a C₇ to C₁₀ benzoyl group. In any aspect disclosed herein, the R²substituted benzoyl group can be a C₇ to C₂₀, a C₁ to C₁₅, or a C₁ toC₁₀ substituted R² benzoyl group. Each substituent of a substitutedalkanoyl group (general or specific), and/or substituted benzoyl group(general or specific) can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a halogen or a hydrocarboxy group; alternatively, ahydrocarbyl group or a hydrocarboxy group; alternatively, a halogen;alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently disclosed herein. These substituent halogens,substituent hydrocarbyl groups, and substituent hydrocarboxy groups canbe utilized without limitation to further describe substituted alkanoylgroups and/or substituted benzoyl group which can be utilized as R².

In an aspect, R² of the N²-phosphinyl amidines and/or the N²-phosphinylamidine transition metal compound complexes can be an alkyl group, asubstituted alkyl group, a cycloalkyl group, a substituted cycloalkylgroup, an aryl group, a substituted aryl group, an aralkyl group, or asubstituted aralkyl group; alternatively, an alkyl group or asubstituted alkyl group; alternatively, a cycloalkyl group or asubstituted cycloalkyl group; alternatively, an aryl group or asubstituted aryl group; alternatively, an aralkyl group or a substitutedaralkyl group; or alternatively, an alkyl group, a cycloalkyl group, anaryl group, or an aralkyl group. In other aspects, R² of theN²-phosphinyl amidine and/or the N²-phosphinyl amidine transition metalcompound complexes can be an alkyl group; alternatively, a substitutedalkyl group, alternatively, a cycloalkyl group; alternatively, asubstituted cycloalkyl group; alternatively, an aryl group;alternatively, a substituted aryl group; alternatively, an aralkylgroup; or alternatively, a substituted aralkyl group. In any aspectdisclosed herein, the R² alkyl group can be a C₁ to C₂₀, a C₁ to C₁₀, ora C₁ to C₅ alkyl group. In any aspect disclosed herein, the R²substituted alkyl group can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅substituted alkyl group. In any aspect disclosed herein, the R²cycloalkyl group can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀cycloalkyl group. In any aspect disclosed herein, the R² substitutedcycloalkyl group can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀substituted cycloalkyl group. In any aspect disclosed herein, the R²aryl group can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ aryl group.In any aspect disclosed herein, the R² substituted aryl group can be aC₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ substituted aryl group. In anyaspect disclosed herein, the R² aralkyl group can be a C₇ to C₂₀, a C₇to C₁₅, or a C₇ to C₁₀ aralkyl group. In any aspect disclosed herein,the R² substituted aryl group can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇to C₁₀ substituted aralkyl group. Each substituent of a substitutedalkyl group (general or specific), a substituted cycloalkyl group(general or specific), a substituted aryl group (general or specific),and/or substituted aralkyl group (general or specific) can be a halogen,a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogenor a hydrocarbyl group; alternatively, a halogen or a hydrocarboxygroup; alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe R².

In an aspect, R² can be a methyl group, an ethyl group, a propyl group,a butyl group, a pentyl group, a hexyl group, a heptyl group, or anoctyl group; or alternatively, a methyl group, an ethyl group, ann-propyl (1-propyl) group, an iso-propyl (2-propyl) group, a tert-butyl(2-methyl-2-propyl) group, or a neopentyl (2,2-dimethyl-1-propyl) group.In some aspects, the alkyl groups which can be utilized as R² can besubstituted. Each substituent of a substituted alkyl group independentlycan be a halogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Substituent halogens andsubstituent hydrocarboxy groups (general and specific) are independentlydisclosed herein. These substituent halogens and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted alkyl group (general or specific) which can beutilized as R².

In an aspect, R² can be a cyclopentyl group, a substituted cyclopentylgroup, a cyclohexyl group, or a substituted cyclohexyl group;alternatively, a cyclopentyl group or a substituted cyclopentyl group;or alternatively, a cyclohexyl group or a substituted cyclohexyl group.In an aspect, the substituted cycloalkyl group, which can be utilized asR², can be a 2-substituted cyclohexyl group, a 2,6-disubstitutedcyclohexyl group, a 2-substituted cyclopentyl group, or a2,5-disubstituted cyclopentyl group; alternatively, a 2-substitutedcyclohexyl group or a 2,6-disubstituted cyclohexyl group; alternatively,a 2-substituted cyclopentyl group or a 2,5-disubstituted cyclopentylgroup; alternatively, a 2-substituted cyclohexyl group or a2-substituted cyclopentyl group; or alternatively, a 2,6-disubstitutedcyclohexyl group or a 2,5-disubstituted cyclopentyl group. In an aspect,one or more substituents of a multi-substituted cycloalkyl grouputilized as R² can be the same or different; alternatively, all thesubstituents of a multi-substituted cycloalkyl group can be the same; oralternatively, all the substituents of a multi-substituted cycloalkylgroup can be different. Each substituent of a cycloalkyl group having aspecified number of ring carbon atoms independently can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted cycloalkyl group (general or specific) which canbe utilized as R².

In a non-limiting aspect. R² can be a cyclohexyl group, a2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group; oralternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describealkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups(general or specific), alkylcyclopentyl groups (general or specific),and/or dialkylcyclopentyl groups (general or specific) which can beutilized as R². Generally, the alkyl substituents of a disubstitutedcyclohexyl or cyclopentyl group can be the same; or alternatively, thealkyl substituents of a dialkyl cyclohexyl or cyclopentyl group can bedifferent. In some non-limiting aspects. R² can be a 2-methylcyclohexylgroup, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group. In other non-limiting aspects, R² canbe, a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group; oralternatively, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexylgroup, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group.

In an aspect, R² can be a phenyl group, a substituted phenyl group;alternatively, a phenyl group; or alternatively, a substituted phenylgroup. In an aspect, the substituted phenyl group, which can be utilizedas R² can be a 2-substituted phenyl group, a 3-substituted phenyl group,a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,or a 2,6-disubstituted phenyl group; alternatively, a 3-substitutedphenyl group or a 3,5-disubstituted phenyl group; alternatively, a2-substituted phenyl group or a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Inan aspect, one or more substituents of a multi-substituted phenyl grouputilized as R² can be the same or different; alternatively, all thesubstituents of a multi-substituted cycloalkyl group can be the same; oralternatively, all the substituents of a multi-substituted cycloalkylgroup can be different. Each substituent of a substituted phenyl group(general or specific) independently can be a halogen, a hydrocarbylgroup, or a hydrocarboxy group; alternatively, a halogen or ahydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted phenyl group (general or specific) which can beutilized as R².

In a non-limiting aspect, R² can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenyl groupor a 2,6-dialkylphenyl group; alternatively, a 3-alkylphenyl group or a3,5-dialkylphenyl group; alternatively, a 2-alkylphenyl group or a2,6-dialkylphenyl group; or alternatively, a 2,4,6-trialkylphenyl group.Alkyl substituent groups (general and specific) are independentlydescribed herein and these alkyl substituent groups can be utilized,without limitation, to further describe any alkyl substituted phenylgroup which can be utilized as R². Generally, the alkyl substituents ofa dialkylphenyl group (general or specific) or trialkylphenyl group(general or specific) can be the same; or alternatively, the alkylsubstituents of a dialkylphenyl group or trialkylphenyl group can bedifferent. In some non-limiting aspects, R² independently can be aphenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a2-n-propylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, aphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group.

In a non-limiting aspect, R² can be a phenyl group, a 2-alkoxyphenylgroup, or a 4-alkoxyphenyl group. In some non-limiting aspects, R² canbe a phenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a 4-methoxyphenylgroup, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenyl group, a2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a2-tert-butoxyphenyl group; or alternatively, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group. In another non-limiting aspect, R² can be aphenyl group, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenyl group. Generally, the halides of a dihalophenyl groupcan be the same; or alternatively, the halides of a dihalophenyl groupcan be different. In some aspects, R² can be a phenyl group, a2-fluorophenyl group, a 4-fluorophenyl group, or a 2,6-difluorophenylgroup.

In an aspect, R² can be a benzyl group or a substituted benzyl group;alternatively, a benzyl group; or alternatively, a substituted benzylgroup. Each substituent of a substituted benzyl group independently canbe a halogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen, alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy groups (general and specific) are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups can be utilized withoutlimitation to further describe a substituted benzyl group which can beutilized as R².

In further aspects. R¹ and R² can be joined to form a ring or a ringsystem containing the carbon-nitrogen double bond of the N²-phosphinylamidines and/or the N²-phosphinyl amidine transition metal compoundcomplexes. The joining of R¹ and R² can be designated as L^(12r) and canbe an organylene group; alternatively, an organylene group consisting ofinert functional groups; alternatively, a hydrocarbylene group; oralternatively, an alkylene group. In an aspect, the L^(12r) organylenegroup, when present, can be a C₃ to C₃₀, a C₃ to C₂₀, a C₃ to C₁₅, or aC₃ to C₁₀ organylene group. In some aspects, the L^(12r) organylenegroup consisting of inert functional groups, when present, can be a C₃to C₃₀, a C₃ to C₂₀, a C₃ to C₁₅, or a C₃ to C₁₀ organylene groupconsisting of inert functional groups. In other aspects, the L^(12r)hydrocarbyl group, when present, independently can be a C₃ to C₃₀, a C₃to C₂₀, a C₃ to C₁₅, or a C₃ to C₁₀ hydrocarbylene group. In a furtheraspect, the L^(12r) alkylene group, when present, independently can be aC₃ to C₃₀, a C₃ to C₂₀, a C₃ to C₁₅, or a C₃ to C₁₀ alkylene group. Inan aspect, L^(12r) can be prop-1,3-ylene group, a but-1,3-ylene group, a3-methylbut-1,3-ylene group (—CH₂CH₂C(CH₃)₂—), a but-1,4-ylene group, a1,4-pent-1,4-ylene group.

Generally, T of the heterocyclic 2-[(phosphinyl)aminyl]imines and/or theheterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplexes can be oxygen or sulfur. In and aspect, T of the heterocyclic2-[(phosphinyl)aminyl]imines and/or the heterocyclic2-[(phosphinyl)aminyl]imine transition metal compound complexes can beoxygen; or alternatively, sulfur.

Generally, R^(2a) and/or R^(2b), of the N²-phosphinyl guanidines and/orthe N²-phosphinyl guanidine transition metal compound complexes whichhave an R^(2a) and/or R^(2b) group, independently can be hydrogen or anorganyl group; alternatively, hydrogen or an organyl group consisting ofinert functional groups; alternatively, hydrogen or a hydrocarbyl group;alternatively, hydrogen; alternatively, an organyl group; alternatively,an organyl group consisting of inert functional groups, oralternatively, a hydrocarbyl group. In an aspect, the R^(2a) and/orR^(2b) organyl groups independently can be a C₁ to C₂₀, a C₁ to C₁₅, aC₁ to C₁₀, or a C₁ to C₅ organyl group. In some aspects, the R^(2a)and/or R^(2b) organyl groups consisting of inert functional groupsindependently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ organyl group consisting of inert functional groups. In otheraspects, the R^(2a) and/or R^(2b) hydrocarbyl groups independently canbe a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ hydrocarbylgroup.

In an aspect, R^(2a) and R^(2b), of the N²-phosphinyl guanidines and/orthe N²-phosphinyl guanidine transition metal compound complexes whichhave an R^(2a) and/or R^(2b) organyl group, independently can be analkyl group, a substituted alkyl group, a cycloalkyl group, asubstituted cycloalkyl group, an aryl group, a substituted aryl group,an aralkyl group, or a substituted aralkyl group; alternatively, analkyl group or a substituted alkyl group; alternatively, a cycloalkylgroup or a substituted cycloalkyl group; alternatively, an aryl group ora substituted aryl group; alternatively, an aralkyl group or asubstituted aralkyl group; alternatively, an alkyl group, a cycloalkylgroup, an aryl group, or an aralkyl group; alternatively, an alkylgroup; alternatively, a substituted alkyl group, alternatively, acycloalkyl group; alternatively, a substituted cycloalkyl group;alternatively, an aryl group; alternatively, a substituted aryl group;alternatively, an aralkyl group; or alternatively, a substituted aralkylgroup. In any aspect disclosed herein, the R^(2a) and/or R^(2b) alkylgroup independently can be C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅ alkylgroup. In any aspect disclosed herein, the R^(2a) and/or R^(2b)cycloalkyl group independently can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄to C₁₀ cycloalkyl group. In any aspect disclosed herein, the R^(2a)and/or R^(2b) substituted cycloalkyl group independently can be a C₄ toC₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ substituted cycloalkyl group. In anyaspect disclosed herein, the R^(2a) and/or R^(2b) aryl groupindependently can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ arylgroup. In any aspect disclosed herein, the R^(2a) and/or R^(2b)substituted aryl group independently can be a C₆ to C₂₀, a C₆ to C₁₅, ora C₆ to C₁₀ substituted aryl group. Each substituent of a substitutedcycloalkyl group (general or specific) and/or a substituted aryl group(general or specific) can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a halogen or a hydrocarboxy group; alternatively, ahydrocarbyl group or a hydrocarboxy group; alternatively, a halogen;alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently disclosed herein. These substituent halogens,substituent hydrocarbyl groups, and substituent hydrocarboxy groups canbe utilized without limitation to further describe R^(2a) and/or R^(2b).

In an aspect. R¹ and R² of the N²-phosphinyl guanidines and/or theN²-phosphinyl guanidine transition metal compound complexes can bejoined to form a group, L¹², wherein L¹², the N¹ nitrogen atom, and theN³ nitrogen atom form a ring or a ring system. In another aspect. R³ andR^(2b) of the N²-phosphinyl guanidines and/or the N²-phosphinylguanidine transition metal compound complexes can be joined to form agroup, L²³, wherein L²³, the N² nitrogen atom, and the N³ nitrogen atomform a ring or a ring system. In an aspect, L¹² and/or L²³, of theN²-phosphinyl guanidines and/or the N²-phosphinyl guanidine transitionmetal compound complexes which have an L¹² group and/or an L²³ group,independently can be an organylene group; alternatively, an organylenegroup consisting of inert functional groups; or alternatively, ahydrocarbylene group. The L¹² and/or L²³ organylene groups independentlycan be a C₂ to C₂₀, a C₂ to C₁₅, a C₂ to C₁₀, or a C₂ to C₅ organylenegroup. The L¹² and/or L²³ organylene groups consisting of inertfunctional groups independently can be a C₂ to C₂₀, a C₂ to C₁₅, a C₂ toC₁₀, or a C₂ to C₅ organylene group consisting of inert functionalgroups. The L¹² and/or L²³ hydrocarbylene groups independently can be aC₂ to C₂₀, a C₂ to C₁₅, a C₂ to C₁₀, or a C₂ to C₅ hydrocarbylene group.

In an aspect, L¹² of the N²-phosphinyl guanidines, the N²-phosphinylguanidine transition metal compound complexes, the heterocyclic2-[(phosphinyl)aminyl]imines and/or the heterocyclic2-[(phosphinyl)aminyl]imine transition metal compound complexes whichhave an L¹² and L²³ of the N²-phosphinyl guanidines and/or theN²-phosphinyl guanidine transition metal compound complexes which havean L²³, can have any structure provided in Table 1. In some aspects, L¹²and/or L²³ can have Structure 1L, Structure 2L, Structure 3L, Structure4L or Structure 5L. In some aspects, L¹² and/or L²³ can have Structure2L or Structure 3L; alternatively, Structure 4L or Structure 5L. Inother aspects, L¹² and/or L²³ can have Structure 1L; alternatively,Structure 2L; alternatively, Structure 3L; alternatively, Structure 4L;or alternatively, Structure 5L. In some N²-phosphinyl guanidine andN²-phosphinyl guanidine transition metal compound complex aspects, L¹²and/or L²³ can have Structure 6L. It should be noted that when L¹² orL²³ has Structure 6L the corresponding R^(2b) or R^(2a) is null becauseof the double bond link with the N³ nitrogen atom of the N²-phosphinylguanidine and/or the N²-phosphinyl guanidine transition metal compoundcomplex.

TABLE 1 Structures for Linking Groups L¹² and/or L²³.—(CR^(L1)R^(L2))_(m)— —CR^(L3)R^(L4)—CR^(L5)R^(L6)— —CR^(L3)R^(L4)—Structure 1L Structure 2L CR^(L7)R^(L8)—CR^(L5)R^(L6)— Structure 3L—CR^(L11)═ CR^(L12)—

═CR^(L27)—CR^(L28)═ CR^(L29) Structure 4L Structure 5L Structure 6L

Within the structures of Table 1, the undesignated valences of L¹²and/or L²³ represent the points at which L¹² and/or L²³, when present,attach to the respective nitrogen atoms of the N²-phosphinyl guanidineand the N²-phosphinyl guanidine transition metal compound complex.Additionally, with the structures of Table 1, the undesignated valencesof L¹² represent the points at which L¹² attach to T and the respectivenitrogen atom of the heterocyclic 2-[(phosphinyl)aminyl]imine and/or theheterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplex. Generally, m can be an integer ranging from 2 to 5. In furtheraspects, m can be 2 or 3; alternatively, m can be 2; or alternatively, mcan be 3. R^(L1) and R^(L2) of the linking group having Structure 1L,R^(L3), R^(L4), R^(L5), and R^(L6) of the linking group having Structure2L, R^(L3), R^(L4), R^(L5), R^(L6), R^(L7), and R^(L8), of the linkinggroup having Structure 3L, R^(L11) and R^(L12) of the linking grouphaving Structure 4L, R^(L23), R^(L24), R^(L25), and R^(L26) of thelinking group having Structure 5L, R^(L27), R^(L28), and R^(L29) of thelinking group having Structure 6L independently can be a hydrogen or anon-hydrogen substituent group; or alternatively, hydrogen. Non-hydrogensubstituent groups (general and specific) are independently disclosedherein and can be utilized without limitation to further describe thelinking group having Structure 1L, Structure 2L, Structure 3L, Structure4L, Structure 5L, and/or Structure 6L. In an aspect, L¹² and/or L²³independently can be an eth-1,2-ylene group (—CH₂CH₂—), anethen-1,2-ylene group (—CH═CH—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), a1-methylethen-1,2-ylene group (—C(CH₃)═CH—), a but-1,3-ylene group(—CH₂CH₂CH(CH)—), a 3-methylbut-1,3-ylene group (—CH₂CH₂C(CH)₂—), or aphen-1,2-ylene group. In some non-limiting aspects, L¹² and/or L²³ be aneth-1,2-ylene group (—CH₂CH₂—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), a1-methylethen-1,2-ylene group (—C(CH₃)═CH—), a but-1,3-ylene group(—CH₂CH₂CH(CH₃)—), or a 3-methylbut-1,3-ylene group (—CH₂CH₂C(CH₃)₂—);alternatively, an eth-1,2-ylene group (—CH₂CH₂—), an ethen-1,2-ylenegroup (—CH═CH—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), or aphen-1,2-ylene group; alternatively, an eth-1,2-ylene group (—CH₂CH₂—)or a prop-1,3-ylene group (—CH₂CH₂CH₂—); alternatively, anethen-1,2-ylene group (—CH═CH—) or a phen-1,2-ylene group.

In an aspect, L¹² can have a structure that can comprise at least onesubstituent located on the carbon atom attached to the N¹ nitrogen atomof the N²-phosphinyl guanidine and/or the N²-phosphinyl guanidinetransition metal compound complex; alternatively, can comprise only onesubstituent located on the carbon atom attached to the N¹ nitrogen atomof the N²-phosphinyl guanidine and/or the N²-phosphinyl guanidinetransition metal compound complex; or alternatively, can comprise twosubstituents located on the carbon atom attached to the N¹ nitrogen atomof the N²-phosphinyl guanidine and/or the N²-phosphinyl guanidinetransition metal compound complex. In another aspect, L¹² can have astructure that can consist of one substituent located on the carbon atomattached to the N¹ nitrogen atom the N²-phosphinyl guanidine and/or theN²-phosphinyl guanidine transition metal compound complex; oralternatively, can consist of two substituents located on the carbonatom attached to the N¹ nitrogen atom of the N²-phosphinyl guanidineand/or the N²-phosphinyl guanidine transition metal compound complex.

In an aspect, R^(2a) and R^(2b) of the N²-phosphinyl guanidines and/orthe N²-phosphinyl guanidine transition metal compound complexes can bejoined to form a group, L²², wherein R^(2a), R^(2b), and the N³ nitrogen(or L²² and the N³ nitrogen) form a ring or ring system. In an aspect,L²² of the N²-phosphinyl guanidines and/or the N²-phosphinyl guanidinetransition metal compound complexes having an L²² group can be anorganylene group; alternatively, an organylene group consisting of inertfunctional groups; or alternatively, a hydrocarbylene group. The L²²organylene group can be a C₃ to C₂₀, a C₃ to C₁₅, or a C₃ to C₁₀organylene group. The L²² organylene group consisting of inertfunctional groups can be a C₃ to C₂₀, a C₃ to C₁₅, or a C₃ to C₁₀organylene group consisting of inert functional groups. The L²²hydrocarbylene group can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀hydrocarbylene group.

In an aspect, L²² can have any structure provided in Table 2. In someaspects, L²² can have Structure 11L, Structure 12L, Structure 13L,Structure 14L, Structure 15L, or Structure 16L. In other aspects, L² canhave Structure 11L; alternatively, Structure 12L; alternatively,Structure 13L; alternatively, Structure 14L; or alternatively, Structure15L.

TABLE 2 Structures for Linking Groups L²². —(CR^(L31)R^(L32))_(n)—Structure 11L —CR^(L41)R^(L42)—CR^(L45)R^(L46) CR^(L47)R^(L48)CR^(L43)R^(L44)— Structure 12L—CR^(L41)R^(L42)—CR^(L45)R^(L46)—CR^(L49)R^(L50)—CR^(L47)R^(L48)—CR^(L43)R^(L44)—Structure 13L—CR^(L41)R^(L42)—CR^(L45)R^(L46)—O—CR^(L47)R^(L48)—CR^(L43)R^(L44)—Structure 14L —CR^(L51)═CR^(L53)—CR^(L54)═CR^(L52)— Structure 15L

Within the structures of Table 2, the undesignated valences representthe points at which L²² of the N²-phosphinyl guanidine and/or theN²-phosphinyl guanidine transition metal compound complex, when present,attach to the N³ nitrogen atom of the N²-phosphinyl guanidine and/or theN²-phosphinyl guanidine transition metal compound complex. Generally, ncan be an integer ranging from 4 to 7. In further aspects, n can be 4 or5; alternatively, n can be 4; or alternatively, n can be 5. R^(L31) andR^(L32) of the linking group having Structure 11L, R^(L41), R^(L42),R^(L43), R^(L44), R^(L45), R^(L46), R^(L47), and R^(L48) of the linkinggroup having Structure 12L, R^(L41), R^(L42), R^(L43), R^(L44), R^(L45),R^(L46), R^(L47), R^(L48), R^(L49), and R^(L50) of the linking grouphaving Structure 13L, R^(L41), R^(L42), R^(L43), R^(L44), R^(L45),R^(L46), R^(L47), and R^(L48) of the linking group having Structure 14L,and R^(L41), R^(L42), R^(L43), R^(L44), R^(L45), R^(L46), R^(L47), andR^(L48) of the linking group having Structure 15L independently can be ahydrogen or a non-hydrogen substituent group; alternatively, hydrogen.Non-hydrogen substituent groups are independently disclosed herein andcan be utilized without limitation to further describe the linking grouphaving Structure 11L, Structure 12L, Structure 13L, Structure 14L,and/or Structure 15L. In an aspect, L²² can be a but-1,4-ylene group, apent-1,4-ylene group, a pent-1,5-ylene group, a hex-2,5-ylene group, ahex-1,5-ylene group, a hept-2,5-ylene group, a buta-1,3-dien-1,4-ylenegroup, or a bis(eth-2-yl)ether group; or alternatively, a but-1,4-ylenegroup, a pent-1,5-ylene group, or a bis(eth-2-yl)ether group.

Generally, R³ of the N²-phosphinyl formamidines, the N²-phosphinylformamidine transition metal compound complexes, the N²-phosphinylamidines, the N²-phosphinyl amidine transition metal compound complexes,the N²-phosphinyl guanidines, the N²-phosphinyl guanidine transitionmetal compound complexes, the heterocyclic 2-[(phosphinyl)aminyl]imines,and/or the heterocyclic 2-[(phosphinyl)aminyl]imine transition metalcompound complexes which have an R³ group can be hydrogen or an organylgroup; hydrogen or an organyl group consisting of inert functionalgroup; alternatively, hydrogen or a hydrocarbyl group; alternatively,hydrogen; alternatively, an organyl group; alternatively, an organylgroup consisting of inert functional group; or alternatively, ahydrocarbyl group. In an aspect, the R³ organyl group can be a C₁ toC₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group. In anaspect, the R³ organyl group consisting of inert functional groups canbe a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl groupconsisting of inert functional groups. In an aspect, the R³ hydrocarbylgroup can be a, a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅hydrocarbyl group. In other aspects, R³ of the N²-phosphinylformamidine, the N²-phosphinyl formamidine transition metal compoundcomplexes, the N²-phosphinyl amidines, the N²-phosphinyl amidinetransition metal compound complexes, the N²-phosphinyl guanidines, theN²-phosphinyl guanidine transition metal compound complexes, theheterocyclic 2-[(phosphinyl)aminyl]imines, and/or the heterocyclic2-[(phosphinyl)aminyl]imine transition metal compound complexes whichhave an R³ group can be a C₁ to C₃₀, a C₁ to C₂₀, a C₁ to C₁₅, a C₁ toC₁₀, or a C₁ to C₅ alkyl group. In yet other aspects, R³ of theN²-phosphinyl formamidine, the N²-phosphinyl formamidine transitionmetal compound complexes, the N²-phosphinyl amidines, the N²-phosphinylamidine transition metal compound complexes, the N²-phosphinylguanidines, the N²-phosphinyl guanidine transition metal compoundcomplexes, the heterocyclic 2-[(phosphinyl)aminyl]imines, and/or theheterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplexes can be a phenyl group or a C₆ to C₂₀ substituted phenyl group;alternatively, a phenyl group or a C₆ to C₁₅ substituted phenyl group;or alternatively, a phenyl group or a C₆ to C₁₀ substituted phenylgroup. Substituent groups (general and specific) are provided herein andthese substituent groups can be utilized to further describe thesubstituted phenyl groups which can be utilized as R³ the N²-phosphinylformamidine, the N²-phosphinyl formamidine transition metal compoundcomplexes, the N²-phosphinyl amidines, the N²-phosphinyl amidinetransition metal compound complexes, the N²-phosphinyl guanidines,and/or the N²-phosphinyl guanidine transition metal compound complexeshaving a non-hydrogen R³ group.

Generally, R⁴ and/or R⁵ of the N²-phosphinyl formamidines, theN²-phosphinyl formamidine transition metal compound complexes, theN²-phosphinyl amidines, the N²-phosphinyl amidine transition metalcompound complexes, the N²-phosphinyl guanidines, the N²-phosphinylguanidine transition metal compound complexes, the heterocyclic2-[(phosphinyl)aminyl]imines, and/or the heterocyclic2-[(phosphinyl)aminyl]imine transition metal compound complexesindependently can be an organyl group; alternatively, an organyl groupconsisting of inert functional groups, or alternatively, a hydrocarbylgroup. In an aspect, the R⁴ and/or R⁵ organyl groups can be a C₁ to C₂₀,a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group. In an aspect, theR⁴ and/or R⁵ organyl groups consisting of inert functional groups can bea C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl groupconsisting of inert functional groups. In an aspect, the R⁴ and/or R⁵hydrocarbyl groups can be a, a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or aC₁ to C₅ hydrocarbyl group. In an aspect, R⁴ and/or R⁵ of theN²-phosphinyl formamidine, the N²-phosphinyl formamidine transitionmetal compound complexes, the N²-phosphinyl amidines, the N²-phosphinylamidine transition metal compound complexes, the N²-phosphinylguanidines, the N²-phosphinyl guanidine transition metal compoundcomplexes, the heterocyclic 2-[(phosphinyl)aminyl]imines, and/or theheterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplexes independently can be an alkyl group, a substituted alkylgroup, a cycloalkyl group, a substituted cycloalkyl group, an arylgroup, a substituted aryl group, an aralkyl group, or a substitutedaralkyl group; alternatively, an alkyl group or a substituted alkylgroup; alternatively, a cycloalkyl group or a substituted cycloalkylgroup; alternatively, an aryl group or a substituted aryl group;alternatively, an aralkyl group or a substituted aralkyl group;alternatively, an alkyl group, a cycloalkyl group, an aryl group, or anaralkyl group; alternatively, an alkyl group; alternatively, asubstituted alkyl group, alternatively, a cycloalkyl group;alternatively, a substituted cycloalkyl group; alternatively, an arylgroup; alternatively, a substituted aryl group; alternatively, anaralkyl group; or alternatively, a substituted aralkyl group.

In any aspect disclosed herein, the R⁴ and/or R⁵ alkyl groupsindependently can be a C₁ to C₂₀, a C₁ to C₁₀, or a C₁ to C₅ alkylgroup. In any aspect disclosed herein, the R⁴ and/or R⁵ substitutedalkyl groups independently can be a C₁ to C₂₀, a C₁ to C₁₀, or C₁ to C₅substituted alkyl group. In any aspect disclosed herein, the R⁴ and/orR⁵ cycloalkyl groups independently can be a C₄ to C₂₀, a C₄ to C₁₅, or aC₄ to C₁₀ cycloalkyl group. In any aspect disclosed herein, the R⁴and/or R⁵ substituted cycloalkyl groups independently can be a C₄ toC₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ substituted cycloalkyl group. In anyaspect disclosed herein, the R⁴ and/or R⁵ aryl groups independently canbe a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ aryl group. In any aspectdisclosed herein, the R⁴ and/or R⁵ substituted aryl group independentlycan be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ substituted aryl group.In any aspect disclosed herein, the R⁴ and/or R⁵ aralkyl groupsindependently can be a C₇ to C₂₀, a C₁ to C₁₅, or a C₇ to C₁₀ aralkylgroup. In any aspect disclosed herein, the R⁴ and/or R⁵ substituted arylgroups independently can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀substituted aralkyl group. Each substituent of a substituted alkyl group(general or specific), a substituted cycloalkyl group (general orspecific), a substituted aryl group (general or specific), and/orsubstituted aralkyl group (general or specific) can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe R⁴ and/or R⁵.

In an aspect, R⁴ and R⁵ independently can be a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, or an octyl group; or alternatively, a methyl group, anethyl group, an n-propyl (1-propyl) group, an iso-propyl (2-propyl)group, a 2-methyl-1-propyl group, a tert-butyl (2-methyl-2-propyl)group, or a neopentyl (2,2-dimethyl-1-propyl) group. In some aspects,the alkyl groups which can be utilized as R⁴ and/or R⁵ can besubstituted. Each substituent of a substituted alkyl group independentlycan be a halogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Substituent halogens andsubstituent hydrocarboxy (general and specific) groups are independentlydisclosed herein. These substituent halogens and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted alkyl group which can be utilized as R⁴ and/orR⁵.

In an aspect, R⁴ and R⁵ independently can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group; alternatively, a cyclopentyl group or a substitutedcyclopentyl group; or alternatively, a cyclohexyl group or a substitutedcyclohexyl group. In an aspect, the substituted cycloalkyl group, whichcan be utilized for R⁴ and/or R⁵, can be a 2-substituted cyclohexylgroup, a 2,6-disubstituted cyclohexyl group, a 2-substituted cyclopentylgroup, or a 2,5-disubstituted cyclopentyl group; alternatively, a2-substituted cyclohexyl group or a 2,6-disubstituted cyclohexyl group;alternatively, a 2-substituted cyclopentyl group or a 2,5-disubstitutedcyclopentyl group; alternatively, a 2-substituted cyclohexyl group or a2-substituted cyclopentyl group; or alternatively, a 2,6-disubstitutedcyclohexyl group or a 2,5-disubstituted cyclopentyl group. In an aspectwhere the substituted cycloalkyl group (general or specific) has morethe one substituent, the substituents can be the same or different;alternatively, the same; or alternatively, different. Each substituentof a cycloalkyl group (general or specific) having a specified number ofring carbon atoms independently can be a halogen, a hydrocarbyl group,or a hydrocarboxy group; alternatively, a halogen or a hydrocarbylgroup; alternatively, a halogen or a hydrocarboxy group; alternatively,a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen,alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently disclosed herein. These substituent halogens,substituent hydrocarbyl groups, and substituent hydrocarboxy groups canbe utilized without limitation to further describe a substitutedcycloalkyl group (general or specific) which can be utilized as R⁴and/or R⁵.

In a non-limiting aspect. R⁴ and R⁵ independently can be a cyclohexylgroup, a 2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group; oralternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describedalkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups(general or specific), alkylcyclopentyl groups (general or specific),and/or dialkylcyclopentyl groups (general or specific) which can beutilized as R⁴ and/or R⁵. Generally, the alkyl substituents of adisubstituted cyclohexyl or cyclopentyl group can be the same; oralternatively, the alkyl substituents of a dialkyl cyclohexyl orcyclopentyl group can be different. In some non-limiting aspects, R⁴ andR⁵ independently can be a 2-methylcyclohexyl group, a 2-ethylcyclohexylgroup, a 2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group.In other non-limiting aspects, R⁴ and R⁵ independently can be, a2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group; oralternatively, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexylgroup, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group.

In an aspect, R⁴ and R⁵ independently can be a phenyl group, asubstituted phenyl group; alternatively, a phenyl group; oralternatively, a substituted phenyl group. In an aspect, the substitutedphenyl group, which can be utilized for R⁴ and/or R⁵, can be a2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,or a 2,6-disubstituted phenyl group; alternatively, a 3-substitutedphenyl group or a 3,5-disubstituted phenyl group; alternatively, a2-substituted phenyl group or a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Inan aspect, one or more substituents of a multi-substituted phenyl grouputilized as R⁴ and/or R⁵ can be the same or different; alternatively,all the substituents of a multi-substituted cycloalkyl group can be thesame; or alternatively, all the substituents of a multi-substitutedcycloalkyl group different. Each substituent of a substituted phenylgroup (general or specific) independently can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted phenyl group (general or specific) which can beutilized as R⁴ and/or R⁵.

Ina non-limiting aspect, R⁴ and R⁵ independently can be a phenyl group,a 2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group a 2,6-dialkylphenyl group, a 3,5-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively,a 2-alkylphenyl group or a 4-alkylphenyl group; alternatively, a2,4-dialkylphenyl group or a 2,6-dialkylphenyl group; alternatively, a3-alkylphenyl group or a 3,5-dialkylphenyl group; alternatively, a2-alkylphenyl group or a 2,6-dialkylphenyl group; or alternatively, a2,4,6-trialkylphenyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describe anyalkyl substituted phenyl group which can be utilized as R⁴ and/or R⁵.Generally, the alkyl substituents of a dialkylphenyl group (general orspecific) or a trialkylphenyl group (general or specific) can be thesame; or alternatively, the alkyl substituents of a dialkylphenyl group(general or specific) or a trialkyl phenyl group (general or specific)can be different. In some non-limiting aspects, R⁴ and R⁵ independentlycan be a phenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a2-n-propylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 26-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, aphenyl group, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group.

In a non-limiting aspect, R⁴ and R⁵ can be a phenyl group, a2-alkoxyphenyl group, or a 4-alkoxyphenyl group. In some non-limitingaspects, R⁴ and/or R⁵ can be a phenyl group, a 2-methoxyphenyl group, a2-ethoxyphenyl group, a 2-isopropoxyphenyl group, a 2-tert-butoxyphenylgroup, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a4-isopropoxyphenyl group, or a 4-tert-butoxyphenyl group; alternatively,a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenylgroup, or a 2-tert-butoxyphenyl group; or alternatively, a4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenylgroup, or a 4-tert-butoxyphenyl group. In a non-limiting aspect. R⁴ andR independently can be a phenyl group, a 2-halophenyl group, a4-halophenyl group, or a 2,6-dihalophenyl group. Generally, the halidesof a dihalophenyl group can be the same; or alternatively, the halidesof a dihalophenyl group can be different. In some aspects, R⁴ and R⁵independently can be a phenyl group, a 2-fluorophenyl group, a4-fluorophenyl group, or a 2,6-difluorophenyl group.

In an aspect, R⁴ and R⁵ independently can be a benzyl group or asubstituted benzyl group; alternatively, a benzyl group; oralternatively, a substituted benzyl group. Each substituent of asubstituted benzyl group independently can be a halogen, a hydrocarbylgroup, or a hydrocarboxy group; alternatively, a halogen or ahydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen, alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted benzyl which can be utilized as R⁴ and/or R⁵.

In further aspects, R⁴ and R⁵ can be joined to form a ring or a ringsystem containing the phosphorus atom. The joining of R⁴ and R⁵ can bedesignated as L⁴⁵ and can be an organylene group; alternatively, anorganylene group consisting of inert functional groups, alternatively, ahydrocarbylene group; or alternatively, an alkylene group. In an aspect,the L⁴⁵ organylene group, when present, can be a C₄ to C₃₀, a C₄ to C₂₀,a C₄ to C₁₅, or a C₄ to C₁₀ organylene group. In an aspect, the L⁴⁵organylene group consisting of inert functional groups, when present,can be a C₄ to C₃₀, a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ organylenegroup consisting of inert functional groups. In an aspect, the L⁴⁵hydrocarbyl group, when present, independently can be a C₄ to C₃₀, a C₄to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ hydrocarbylene group. In a furtheraspect, the L⁴⁵ alkylene group, when present, independently can be a C₄to C₃₀, a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ alkylene group. In anaspect, L⁴⁵ can be a but-1,4-ylene group, a 1,4-diphenylbut-1,4-ylenegroup, a 1,4-di(2-methylphenyl)but-1,4-ylene group,1,4-di(4-methylphenyl)but-1,4-ylene group,1,4-di(4-t-butylphenyl)but-1,4-ylene group, a1,4-di(3,5-dimethylphenyl)but-1,4-ylene group, a pent-1,4-ylene group, a1-phenylpenta-1,4-ylene group, a 4-phenylpenta-1,4-ylene group, ahex-2,5-ylene group, a 2,2′-biphenylene group, a2,2′-(methandiyl)dipheylene group, or a 2,2′-(1,2-ethandiyl)diphenylenegroup.

In an aspect, the heteroatomic ligand or the heteroatomic ligand of theheteroatomic ligand transition metal compound complex can have theformula (R^(1s))_(m)X^(1s)(L^(1s))X^(2s)(R^(2s))_(n) while theheteroatomic ligand transition metal compound complex can have theformula:

In some aspects, the heteroatomic ligand or the heteroatomic ligand ofthe heteroatomic ligand transition metal compound complex can have twogroups capable of being described by the formula(R^(1s))_(m)X^(1s)(L^(1s))X^(2s)(R^(2s))_(n). In instances wherein theheteroatomic ligand can have two groups capable of being described bythe formula (R^(1s))_(m)X^(1s)(L^(1s))X^(2s)(R^(2s))_(n), the two L^(1s)groups are linked and the heteroatomic ligand and the heteroatomicligand transition metal compound complex can have the formulas:

respectively.

In the heteroatomic ligand or the heteroatomic ligand of theheteroatomic ligand transition metal compound complex having formula(R^(1s))_(m)X^(1s)(L^(1s))X^(2s)(R^(2s))_(n) or having two linked(R^(1s))_(m)X^(1s)(L^(1s))X^(2s)(R^(2s))_(n) groups, each X^(1s) andeach X^(2s) independently can be selected from the group consisting ofN, P, O, and S; each L^(1s) can be an independent linking group betweenthe respective X^(1s)s and X^(2s)s; each m and each n independently canbe 1 or 2; and each R^(1s) and each R^(2s) independently can be ahydrogen, an organyl group (or alternatively, an organyl groupconsisting of inert functional group; or alternatively, a hydrocarbylgroup), or a heterohydrocarbyl group, where when there are two or moreR^(1s)s and/or two R^(2s)s, each R^(1s) can be the same or different(alternatively, the same; or alternatively, different) and/or eachR^(2s) can be the same or different (alternatively, the same; oralternatively, different). L^(1s), X^(1s), X^(2s), R^(1s), R^(2s), m,and n are independent elements of any heteroatomic ligand or anyheteroatomic ligand of the heteroatomic ligand transition metal compoundcomplex which have an L^(1s), X^(1s), X^(2s), R^(1s), R^(2s), m, and/orn and are independently described herein. These independent descriptionsof L^(1s), X^(1s), X^(2s), R^(1s), R^(2s), m, and n can be utilizedwithout limitation, and in any combination, to further describe anyheteroatomic ligand or any heteroatomic ligand of the heteroatomicligand transition metal compound complex which have an L^(1s), X^(1s),X^(2s), R^(1s), R^(2s), m, and/or n. Additionally, CrX_(p) is anindependent element of the heteroatomic ligand transition metal compoundcomplex, and is independently described herein, and can be utilizedwithout limitation, and in any combination with L^(1s), X^(1s), X^(2s),R^(1s), R^(2s), m, and n of the heteroatomic ligand to further describethe heteroatomic ligand transition metal compound complexes contemplatedherein.

In an aspect, each X^(1s) and each X^(2s) of any heteroatomic ligand orany heteroatomic ligand of any heteroatomic ligand transition metalcompound complex described herein having an X_(1s) and/or X^(2s) can beindependently selected from N, P. O, and S; alternatively, independentlyselected from N and P; or alternatively, independently selected from Oand S. In some aspects, each X^(1s) and each X^(2s) can be N;alternatively, P; alternatively, O; or alternatively, S. Each m and eachn of any heteroatomic ligand or any heteroatomic ligand of anyheteroatomic ligand transition metal compound complex described hereinhaving an m and/or n can be independently selected from 1 or 2;alternatively, 1; or alternatively, 2. Is some particular aspects, eachm and/or each n can be 1 when X^(1s) and/or X^(2s), respectively, is Oor S; alternatively, O; or alternatively, S. In some other particularaspects, each m and/or each n can be 2 when X^(1s) and/or X^(2s),respectively, is N or P; alternatively, N; or alternatively, P.

In a non-limiting aspect, the heteroatomic ligand can have the formulaR^(1s)S(L^(1s))SR^(2s), (R^(1s))₂P(L^(1s))P(R^(2s))₂, or(R^(1s))₂N(L^(1s))N(R^(2s))₂; alternatively, R^(1s)S(L^(1s))SR^(2s);alternatively, (R^(1s))₂P(L^(1s))P(R^(2s))₂; or alternatively,(R^(1s))₂N(L^(1s))N(R^(2s))₂ while the heteroatomic ligand transitionmetal compound complex can have any one of the formulas

In non-limiting aspects where the heteroatomic ligand or theheteroatomic ligand of the heteroatomic ligand transition metal compoundcomplex has two linked heteroatomic groups, the heteroatomic ligand canhave the formula selected from one or more of

while the heteroatomic ligand transition metal compound complex can haveany one of the formulas

In an aspect, each L^(1s) of any heteroatomic ligand or any heteroatomicligand of the heteroatomic ligand transition metal compound complexdescribed herein independently can be any group capable of linking groupX^(1s) and X^(2s) (and other L^(1s) group when the heteroatomic ligandor heteroatomic ligand of the heteroatomic ligand transition metalcompound complex when there are more than one L^(1s) group). In someaspects, each LIS independently can be an organylene group, anamin-di-yl group, or a phosphin-di-yl group; alternatively, anorganylene group consisting of inert functional groups, an amin-di-ylgroup, or a phosphin-di-yl group; alternatively, a hydrocarbylene group,an amin-di-yl group, or a phosphin-di-yl group; alternatively anamin-di-yl group or a phosphin-di-yl group; alternatively, an organylenegroup; alternatively, an organylene group consisting of inert functionalgroups; alternatively, a hydrocarbylene group; alternatively, anamin-di-yl group; or alternatively, a phosphin-di-yl group. When thereis more than one L^(1s) group in the heteroatomic ligand or heteroatomicligand of the heteroatomic ligand transition metal compound complex eachL^(1s) independently can be an organic, an amine group, or a phosphinegroup; alternatively, an organic group consisting of inert functionalgroups, an amine group, or a phosphine group; alternatively, ahydrocarbon group, an amine group, or a phosphine group; alternativelyan amine group or a phosphine group; alternatively, an organic group;alternatively, an organic group consisting of inert functional groups;alternatively, a hydrocarbon group; alternatively, an amine group; oralternatively, a phosphine group. In an aspect, the L^(1s) organylenegroup or organic group can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or,a C₁ to C₅ organylene or organic group. In an aspect, the L^(1s)organylene group consisting of inert functional groups can be a C₁ toC₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or, a C₁ to C₅ organylene or organicgroup consisting of inert functional groups. In an aspect, the L^(1s)hydrocarbylene group can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or aC₁ to C₅ hydrocarbylene or hydrocarbon group. In an aspect, theamin-di-yl or amine group can be a C₁ to C₃₀, a C₁ to C₂₀, a C₁ to C₁₅,or a C₁ to C₁₀ amin-di-yl or amine group. In an aspect, thephosphin-di-yl or phosphine group can be a C₁ to C₃₀, a C₁ to C₂₀, a C₁to C₁₅, or a C₁ to C₁₀ phosphin-di-yl or phosphine group.

In an aspect, each L^(1s) organylene or organic group can have theformula -(L^(3s))NR^(5s)(L^(4s))- or -(L^(3s))PR^(5s)(L^(4s))-;alternatively, -(L^(3s))NR^(5s)(L^(4s))-; or alternatively,-(L^(3s))PR^(5s)(L^(4s))-. In an aspect, the each amin-di-yl group canhave the formula —N(R^(5s))—. In an aspect, each phosphin-di-yl groupcan have the formula —P(R^(5s))—. In these L^(1s) group formulas, thedashes represent the undesignated valance to which the X^(1s) and X^(2s)of the heteroatomic ligand or the heteroatomic ligand of theheteroatomic ligand of the heteroatomic ligand transition metal compoundcomplex described herein attach. When there is more than one L^(1s)group in the heteroatomic ligand or heteroatomic ligand of theheteroatomic ligand transition metal compound complex, the R^(5s) ofeach L_(1s) group can be combined into a linking group designated asL^(2s). In some non-limiting aspects, the heteroatomic ligand can haveStructure PNP1, Structure PNP2, Structure NRNRN, Structure PRPRP,Structure SRNRS, Structure PRNRP, and Structure NRPRN; alternatively,Structure PNP1 or Structure PNP2; alternatively, Structure PRPRP,Structure SRNRS, or Structure PRNRP; alternatively, Structure PNP;alternatively, Structure PNP2; alternatively, Structure NRNRN;alternatively, Structure PRPRP; alternatively, Structure SRNRS;alternatively, Structure PRNRP; or alternatively, Structure NRPRN. Insome non-limiting aspects, the heteroatomic ligand transition metalcompound complex having a heteroatomic ligand(R^(1s))_(m)X^(1s)(L^(1s))X^(2s)(R^(2s))_(n), which can be utilized incatalyst systems described herein can have Structure PNPM1, StructurePNPM2, Structure NRNRNM1, Structure PRPRPCr1, Structure SRNRSM1,Structure PRNRPC-1r, and Structure NRPRNM1; alternatively, StructurePNPM1 or Structure PNPM2; alternatively, Structure PRPRPM1, StructureSRNRSM1, or Structure PRNRPC-1r; alternatively, Structure PNPM1;alternatively, Structure PNPM2; alternatively, Structure NRNRNC-1r;alternatively, Structure PRPRPM1; alternatively, Structure SRNRSM1;alternatively, Structure PRNRPM1; or alternatively, Structure NRPRNC-1r.

The R^(5s), L^(2s), L^(3s), L^(4s), R^(11s), R^(12s), R^(13s), andR^(14s) are each independent elements of the heteroatomic ligands havingStructure PNP1, Structure PNP2, Structure NRNRN1, Structure PRPRP1,Structure SRNRS1. Structure PRNRP1, or Structure NRPRN1, and/or theheteroatomic ligand of the heteroatomic ligand transition metal compoundcomplexes having Structure PNPM1, Structure PNPM2, Structure NRNRNM1,Structure PRPRPM1, Structure SRNRSM1, Structure PRNRPM1, and StructureNRPRNM1 in which they occur and are independently described herein. Theindependent descriptions of R^(5s), L^(2s), L^(3s), L^(4s), R^(11s),R^(12s), R^(13s), and R^(14s) can be utilized without limitation, and inany combination, to further describe the heteroatomic ligand structuresand/or the heteroatomic ligand transition metal compound complexstructure in which they occur. Similarly, X and p are independentelements of the heteroatomic ligand transition metal compound complexeshaving Structure PNPM1, Structure PNPM2, Structure NRNRNM1, StructurePRPRPM1, Structure SRNRSM1, Structure PRNRPM1, and Structure NRPRNM1 andare independently described herein. The independent description of X andp can be utilized without limitation, and in any combination, with theindependently described R^(5s), L^(2s), L^(3s), L^(4s), R^(11s),R^(12s), R^(13s), and R^(14s) provided herein to further describe anyheteroatomic ligand transition metal compound complex having StructurePNPM1, Structure PNPM2, Structure NRNRNM1, Structure PRPRPM1, StructureSRNRSM1, Structure PRNRPM1, and/or Structure NRPRNM1.

Generally, R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s), ofany heteroatomic ligand structure depicted herein and/or anyheteroatomic ligand transition metal compound complex depicted hereinhaving an R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)group, independently can be an organyl group; alternatively, an organylgroup consisting of inert functional groups; or alternatively, ahydrocarbyl group. In an aspect, the organyl group which can be utilizedas R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)independently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ organyl group. In an aspect, the organyl group consisting of inertfunctional groups which can be utilized as R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and/or R^(14s) independently can be a C₁ to C₂₀, a C₁to C₁₅, a C₁ to C₁₀, or a C₁ to C₅ organyl group consisting of inertfunctional groups. In an aspect, the hydrocarbyl group which can beutilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)independently can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ toC₅ hydrocarbyl group.

In an aspect, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) of any heteroatomic ligand structure depicted herein and/or anyheteroatomic ligand transition metal compound complex depicted hereinhaving an R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)group independently can an alkyl group, a substituted alkyl group, acycloalkyl group, a substituted cycloalkyl group, an aryl group, asubstituted aryl group, an aralkyl group, or a substituted aralkylgroup; alternatively, an alkyl group or a substituted alkyl group;alternatively, a cycloalkyl group or a substituted cycloalkyl group;alternatively, an aryl group or a substituted aryl group; alternatively,an aralkyl group or a substituted aralkyl group; or alternatively, analkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Inother aspects, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) of any heteroatomic ligand structure depicted herein and/or anyheteroatomic ligand transition metal compound complex depicted hereinhaving an R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)group independently can be an alkyl group; alternatively, a substitutedalkyl group, alternatively, a cycloalkyl group; alternatively, asubstituted cycloalkyl group; alternatively, an aryl group;alternatively, a substituted aryl group; alternatively, an aralkylgroup; or alternatively, a substituted aralkyl group.

In any aspect disclosed herein, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) alkyl group independently can be a C₁ to C₂₀, aC₁ to C₁₀, or a C₁ to C₅ alkyl group. In any aspect disclosed herein,each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)substituted alkyl group independently can be a C₁ to C₂₀, a C₁ to C₁₀,or a C₁ to C₅ substituted alkyl group. In any aspect disclosed herein,each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)cycloalkyl group independently can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄to C₁₀ cycloalkyl group. In any aspect disclosed herein, each R^(1s),R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s) substituted cycloalkylgroup independently can be a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀substituted cycloalkyl group. In any aspect disclosed herein, eachR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s) aryl groupindependently can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ arylgroup. In any aspect disclosed herein, each R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and/or R^(14s) substituted aryl group independentlycan be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀ substituted aryl group.In any aspect disclosed herein, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) aralkyl group independently can be a C₇ to C₂₀,a C₇ to C₁₅, or a C₇ to C₁₀ aralkyl group. In any aspect disclosedherein, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)substituted aralkyl group independently can be a C₇ to C₂₀, a C₇ to C₁₅,or a C₇ to C₁₀ substituted aralkyl group. Each substituent of asubstituted alkyl group (general or specific), a substituted cycloalkylgroup (general or specific), a substituted aryl group (general orspecific), and/or substituted aralkyl group (general or specific) can bea halogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively,a halogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarboxy groups, and substituenthydrocarboxy groups can be utilized without limitation to furtherdescribe a substituted group (general or specific) which can be utilizedR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s).

In an aspect, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, oran octyl group; or alternatively, a methyl group, an ethyl group, aniso-propyl (2-propyl) group, a tert-butyl (2-methyl-2-propyl) group, ora neopentyl (2,2-dimethyl-1-propyl) group. In some aspects, the alkylgroups which can be utilized as each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) independently can be substituted. Eachsubstituent of a substituted alkyl group independently can be a halogenor a hydrocarboxy group; alternatively, a halogen; or alternatively, ahydrocarboxy group. Substituent halogens and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens and substituent hydrocarboxy groups can be utilizedwithout limitation to further describe a substituted alkyl group(general or specific) which can be utilized as R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and/or R^(14s).

In an aspect, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) independently can be a cyclopentyl group, a substitutedcyclopentyl group, a cyclohexyl group, or a substituted cyclohexylgroup; alternatively, a cyclopentyl group or a substituted cyclopentylgroup; or alternatively, a cyclohexyl group or a substituted cyclohexylgroup; alternatively, a cyclopentyl group; alternatively, a substitutedcyclopentyl group; alternatively, a cyclohexyl group; or alternatively,a substituted cyclohexyl group. In an aspect, the substituted cycloalkylgroup, which can be utilized for any of R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and/or R^(14s), when present in any heteroatomicligand described herein, any heteroatomic ligand of the heteroatomicligand transition metal compound complex described herein, anyheteroatomic ligand formula or structure provided herein, and/or anyheteroatomic ligand transition metal compound complex structure providedherein, independently can be a 2-substituted cyclohexyl group, a2,6-disubstituted cyclohexyl group, a 2-substituted cyclopentyl group,or a 2,5-disubstituted cyclopentyl group; alternatively, a 2-substitutedcyclohexyl group or a 2,6-disubstituted cyclohexyl group; alternatively,a 2-substituted cyclopentyl group or a 2,5-disubstituted cyclopentylgroup; alternatively, a 2-substituted cyclohexyl group or a2-substituted cyclopentyl group; or alternatively, a 2,6-disubstitutedcyclohexyl group or a 2,5-disubstituted cyclopentyl group. In an aspect,one or more substituents of a multi-substituted cycloalkyl grouputilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)can be the same or different; alternatively, all the substituents of amulti-substituted cycloalkyl group can be the same; or alternatively,all the substituents of a multi-substituted cycloalkyl group can bedifferent. Each substituent of a substituted cycloalkyl group (generalor specific) having a specified number of ring carbon atomsindependently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen, alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups (general and specific), andsubstituent hydrocarboxy groups (general and specific) are independentlydisclosed herein. These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups can be utilized withoutlimitation to further describe a substituted cycloalkyl group (generalor specific) which can be utilized as R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s).

In a non-limiting aspect, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) independently can be a cyclohexyl group, a2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group; oralternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describealkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups(general or specific), alkylcyclopentyl groups (general or specific),and/or dialkylcyclopentyl groups (general or specific) which can beutilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R¹⁴.Generally, the alkyl substituents of a disubstituted cyclohexyl orcyclopentyl group can be the same, or alternatively, the alkylsubstituents can be different. In some non-limiting aspects, eachR^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and R^(14s), when present inany heteroatomic ligand described herein, any heteroatomic ligand of theheteroatomic ligand transition metal compound complex described herein,any heteroatomic ligand formula or structure provided herein, and/or anyheteroatomic ligand transition metal compound complex structure providedherein, independently can be a 2-methylcyclohexyl group, a2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group; alternatively, a 2-methylcyclohexylgroup, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a2-tert-butylcyclohexyl group; or alternatively, a 2,6-dimethylcyclohexylgroup, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group,or a 2,6-di-tert-butylcyclohexyl group.

In an aspect, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) independently can be a phenyl group or a substituted phenylgroup; alternatively, a phenyl group; or alternatively, a substitutedphenyl group. In an aspect, the substituted phenyl group which can beutilized for each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s), when present in any heteroatomic ligand described herein, anyheteroatomic ligand of the heteroatomic ligand transition metal compoundcomplex described herein, any heteroatomic ligand formula or structureprovided herein, and/or any heteroatomic ligand transition metalcompound complex structure provided herein, independently can be a2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,or a 2,6-disubstituted phenyl group; alternatively, a 3-substitutedphenyl group or a 3,5-disubstituted phenyl group; alternatively, a2-substituted phenyl group or a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; alternatively, a 2-substituted phenyl group;alternatively, a 3-substituted phenyl group; alternatively, a4-substituted phenyl group; alternatively, a 2,4-disubstituted phenylgroup; alternatively, a 2,6-disubstituted phenyl group; alternatively, a3,5-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstitutedphenyl group. In an aspect, one or more substituents of amulti-substituted phenyl group utilized as R^(1s), R^(2s), R^(11s),R^(12s), R^(13s), and/or R^(14s) can be the same or different;alternatively, all the substituents can be the same; or alternatively,all the substituents can be different. Each substituent of a substitutedphenyl group (general or specific) independently can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups (general and specific), and substituent hydrocarboxygroups (general and specific) are independently disclosed herein. Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy group can be utilized without limitation to furtherdescribe a substituted phenyl group (general or specific) which can beutilized as R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s).

In a non-limiting aspect, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) independently can be a phenyl group, a2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively,a 2-alkylphenyl group or a 4-alkylphenyl group; alternatively, a2,4-dialkylphenyl group or a 2,6-dialkylphenyl group; alternatively, a3-alkylphenyl group or a 3,5-dialkylphenyl group; alternatively, a2-alkylphenyl group or a 2,6-dialkylphenyl group; or alternatively, a2,4,6-trialkylphenyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describe anyalkyl substituted phenyl group which can be utilized as R^(1s), R^(2s),R^(11s), R^(12s), R^(13s), and/or R^(14s). Generally, the alkylsubstituents of dialkyIphenyl groups (general or specific) ortrialkylphenyl groups (general or specific) can be the same, oralternatively, the alkyl substituents can be different. In somenon-limiting aspects, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s),and/or R^(14s), when present in any heteroatomic ligand describedherein, any heteroatomic ligand of the heteroatomic ligand transitionmetal compound complex described herein, any heteroatomic ligand formulaor structure provided herein, and/or any heteroatomic ligand transitionmetal compound complex structure provided herein, independently can be aphenyl group, a 2-methylphenyl group, a 2-ethylphenyl group, a2-n-propylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, a phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; oralternatively, a phenyl group, a 2,6-dimethylphenyl group, a2,6-diethylphenyl group, a 2,6-di-n-propylphenyl group, a2,6-diisopropylphenyl group, a 2,6-di-tert-butylphenyl group, a2-isopropyl-6-methylphenyl group, or a 2,4,6-trimethylphenyl group.

In a non-limiting aspect, each R^(1s), R^(2s), R^(11s), R^(12s),R^(13s), and/or R^(14s) independently can be a phenyl group, a2-alkoxyphenyl group, or a 4-alkoxyphenyl group. In some non-limitingaspects, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s),when present in any heteroatomic ligand described herein, anyheteroatomic ligand of the heteroatomic ligand transition metal compoundcomplex described herein, any heteroatomic ligand formula or structureprovided herein, and/or any heteroatomic ligand transition metalcompound complex structure provided herein, independently can be aphenyl group, a 2-methoxyphenyl group, a 2-ethoxyphenyl group, a2-isopropoxyphenyl group, a 2-tert-butoxyphenyl group, a 4-methoxyphenylgroup, a 4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenyl group, a2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a2-tert-butoxyphenyl group; or alternatively, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group. In a non-limiting aspect, each R^(1s),R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s) independently can be aphenyl group, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenyl group. Generally, the halides of a dihalophenyl groupcan be the same, or alternatively, the halides can be different. In someaspects, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/or R^(14s)independently can be a phenyl group, a 2-fluorophenyl group, a4-fluorophenyl group, or a 2,6-difluorophenyl group.

In an aspect, each R^(1s), R^(2s), R^(11s), R^(12s), R^(13s), and/orR^(14s) independently can be a benzyl group or a substituted benzylgroup; alternatively, a benzyl group; or alternatively, a substitutedbenzyl group. Each substituent of a substituted benzyl group (general orspecific) independently can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a halogen or a hydrocarboxy group; alternatively, ahydrocarbyl group or a hydrocarboxy group; alternatively, a halogen,alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently disclosed herein. These substituent halogens,substituent hydrocarbyl groups, and substituent hydrocarboxy groups canbe utilized without limitation to further describe a substituted benzylgroup (general or specific) which can be utilized as R^(1s), R^(2s),R^(11s), R^(12s), R^(13s), and/or R^(14s).

In further aspects, two geminal RNs, two geminal R^(2s)s, geminalR^(11s) and R^(12s), and/or geminal R^(13s) and R^(14s) independentlycan be joined to form a ring or a ring system containing the heteroatomto which they are attached. The joining of two geminal R^(1s)s can bedesignated L^(11s). The joining of two geminal R^(2s)s can be designatedL^(22s). The joining of geminal R^(11s) and R^(12s) can be designatedL^(12s). The joining of geminal R^(13s) and R^(14s) can be designatedL^(34s). In an aspect, L^(11s), L^(22s), L^(12s), and/or L^(34s)independently can be an organylene group; alternatively, an organylenegroup consisting of inert functional groups; alternatively, ahydrocarbylene group; or alternatively, an alkylene group. In an aspect,the L^(11s), L^(22s), L^(12s), and/or L^(34s) organylene group, whenpresent, independently can be a C₄ to C₃₀, a C₄ to C₂₀, a C₄ to C₁₅, ora C₄ to C₁₀ organylene group. In some aspects, the L^(11s), L^(22s),L^(12s), and/or L^(34s) organylene group consisting of inert functionalgroups, when present, independently can be a C₄ to C₃₀, a C₄ to C₂₀, aC₄ to C₁₅, or a C₄ to C₁₀ organylene group consisting of inertfunctional groups. In other aspects, the L^(11s), L^(12s), L^(12s),and/or L^(34s) hydrocarbyl group, when present, independently can be aC₄ to C₃₀, a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ hydrocarbylenegroup. In a further aspect, the L^(11s), L^(12s), L^(12s), and/orL^(34s) alkylene group, when present, independently can be a C₄ to C₃₀,a C₄ to C₂₀, a C₄ to C₁₅, or a C₄ to C₁₀ alkylene group. In an aspect,L^(12s) and/or L^(34s), when present, independently can be a can bebut-1,4-ylene group, a 1,4-diphenylbut-1,4-ylene group, a1,4-di(2-methylphenyl)but-1,4-ylene group,1,4-di(4-methylphenyl)but-1,4-ylene group,1,4-di(4-t-butylphenyl)but-1,4-ylene group, a1,4-di(3,5-dimethylphenyl)but-1,4-ylene group, a pent-1,4-ylene group, a1-phenylpenta-1,4-ylene group, a 4-phenylpenta-1,4-ylene group, ahex-2,5-ylene group, a 2,2′-biphenylene group, a2,2′-(methandiyl)diphenylene group, or a 2,2′-(1,2-ethandiyl)diphenylenegroup.

Generally, R^(5s), of any heteroatomic ligand structure depicted hereinand any heteroatomic ligand transition metal compound complex depictedherein having an R^(5s) group, can be an organyl group; alternatively,an organyl group consisting of inert functional groups; oralternatively, a hydrocarbyl group. In an aspect, the R^(5s) organylgroup can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, or a C₁ to C₅organyl group. In an aspect, the R^(5s) organyl group consisting ofinert functional groups can be a C₁ to C₂₀, a C₁ to C₁₅, a C₁ to C₁₀, ora C₁ to C₅ organyl group consisting of inert functional groups. In anaspect, the R^(5s) hydrocarbyl group can be a C₁ to C₂₀, a C₁ to C₁₅, aC₁ to C₁₀, or a C₁ to C₅ hydrocarbyl group.

In an aspect, R^(5s), of any heteroatomic ligand structure depictedherein and any heteroatomic ligand transition metal compound complexdepicted herein having an R^(5s) group, can be an alkyl group, asubstituted alkyl group, a cycloalkyl group, a substituted cycloalkylgroup, an aryl group, a substituted aryl group, an aralkyl group, or asubstituted aralkyl group; can be an alkyl group or a substituted alkylgroup; alternatively, a cycloalkyl group or a substituted cycloalkylgroup; alternatively, an aryl group or a substituted aryl group;alternatively, an aralkyl group or a substituted aralkyl group; oralternatively, an alkyl group, a cycloalkyl group, an aryl group, or anaralkyl group. In other aspects, R^(5s) of any heteroatomic ligandstructure depicted herein and any heteroatomic ligand transition metalcompound complex depicted herein having an R^(5s) group, can be an alkylgroup; alternatively, a substituted alkyl group, alternatively, acycloalkyl group; alternatively, a substituted cycloalkyl group;alternatively, an aryl group; alternatively, a substituted aryl group;alternatively, an aralkyl group; or alternatively, a substituted aralkylgroup. In any aspect disclosed herein, the R^(5s) alkyl group can be aC₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ alkyl group. In any aspectdisclosed herein, the R^(5s) substituted alkyl group can be a C₁ to C₂₀,a C₁ to C₁₅, or a C₁ to C₁₀ substituted alkyl group. In any aspectdisclosed herein, the R^(5s) cycloalkyl group can be a C₄ to C₂₀, a C₄to C₁₅, or a C₄ to C₁₀ cycloalkyl group. In any aspect disclosed herein,the R^(5s) substituted cycloalkyl group can be a C₄ to C₂₀, a C₄ to, ora C₄ to C₁₀ substituted cycloalkyl group. In any aspect disclosedherein, the R^(5s) aryl group can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆to C₁₀ aryl group. In any aspect disclosed herein, the R^(5s)substituted aryl group can be a C₆ to C₂₀, a C₆ to C₁₅, or a C₆ to C₁₀substituted aryl group. In any aspect disclosed herein, the R^(5s)aralkyl group can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀ aralkylgroup. In any aspect disclosed herein, the R^(5s) substituted aralkylgroup can be a C₇ to C₂₀, a C₇ to C₁₅, or a C₇ to C₁₀ substitutedaralkyl group. Each substituent of a substituted alkyl group (general orspecific), substituted cycloalkyl group (general or specific),substituted aryl group (general or specific), and/or substituted aralkylgroup (general or specific) can be a halogen, hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a halogen or a hydrocarboxyl group; alternatively, ahydrocarbyl group or a hydrocarboxy group; alternatively, a halogen;alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, hydrocarbyl groups (general and specific),and substituent hydrocarboxy groups (general and specific) areindependently disclosed herein. These substituent halogens, substituenthydrocarbyl groups, and substituent hydrocarboxy groups can be utilizedwithout limitation to further describe a substituted group (general orspecific) which can be utilized R^(5s).

In an aspect, R^(5s) can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, oran octyl group; alternatively, a methyl group, an ethyl group, ann-propyl (1-propyl) group, an isopropyl (2-propyl) group, an n-butyl(1-butyl) group, a sec-butyl (2-butyl) group, an isobutyl(2-methyl-1-propyl) group, a tert-butyl (2-methyl-2-propyl) group, ann-pentyl (1-pentyl) group, a 2-pentyl group, a 3-pentyl group, a2-methyl-1-butyl group, a tert-pentyl (2-methyl-2-butyl) group, a3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl(2,2-dimethyl-1-propyl) group; or alternatively, a methyl group, anethyl group, an iso-propyl (2-propyl) group, a tert-butyl(2-methyl-2-propyl) group, or a neopentyl (2,2-dimethyl-1-propyl) group.In some aspects, the R^(5s) alkyl groups can be substituted. Eachsubstituent of a R^(5s) substituted alkyl group independently can be ahalogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Substituent halogens andsubstituent hydrocarboxy groups (general and specific) are independentlydescribed herein and these substituent groups can be utilized withoutlimitation to further describe a substituted alkyl group (general orspecific) which can be utilized as R^(5s).

In an aspect, R^(5s) can be a cyclopentyl group, a substitutedcyclopentyl group, a cyclohexyl group, a substituted cyclohexyl group;alternatively, a cyclopentyl group or a substituted cyclopentyl group;or alternatively, a cyclohexyl group or a substituted cyclohexyl group.In further aspects. R^(5s) can be a 2-substituted cyclohexyl group, a2,6-disubstituted cyclohexyl group, a 2-substituted cyclopentyl group,or a 2,5-disubstituted cyclopentyl group; alternatively, a 2-substitutedcyclohexyl group or a 2,6-disubstituted cyclohexyl group; alternatively,a 2-substituted cyclohexyl group or a 2,6-disubstituted cyclohexylgroup; alternatively, a 2-substituted cyclopentyl group or a2,5-disubstituted cyclopentyl group; alternatively, a 2-substitutedcyclohexyl group or a 2-substituted cyclopentyl group; or alternatively,a 2,6-disubstituted cyclohexyl group or a 2,5-disubstituted cyclopentylgroup. In an aspect, one or more substituents of a multi-substitutedcycloalkyl group utilized as R can be the same or different;alternatively, all the substituents of a multi-substituted cycloalkylgroup can be the same; or alternatively, all the substituents of amulti-substituted cycloalkyl group can be different. Each substituent ofa cycloalkyl group (general or specific) having a specified number ofring carbon atoms independently can be a halogen, a hydrocarbyl group,or a hydrocarboxy group; alternatively, a halogen or a hydrocarbylgroup; alternatively, a halogen or a hydrocarboxy group; alternatively,a hydrocarbyl group or a hydrocarboxy group; alternatively, a halogen;alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently described herein and these substituent groups can beutilized without limitation to further describe a substituted cycloalkylgroup (general or specific) which can be utilized as R^(5s).

In a non-limiting aspect, R^(5s) can be a cyclohexyl group, a2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group; oralternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group. Alkyl substituent groups (general andspecific) are independently described herein and these alkyl substituentgroups can be utilized, without limitation, to further describealkylcyclohexyl groups (general or specific), dialkylcyclohexyl groups(general or specific), alkylcyclopentyl groups (general or specific),and/or dialkylcyclopentyl groups (general or specific) which can beutilized as R^(5s). Generally, the alkyl substituents of a disubstitutedcyclohexyl or cyclopentyl group can be the same, or alternatively, thealkyl substituents can be different. In some non-limiting aspects,R^(5s) heteroatomic ligand structure provided herein, and/or anyheteroatomic ligand transition metal compound complex structure providedherein can be a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group.In other non-limiting aspects, R^(5s) can be a 2-methylcyclohexyl group,a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a2-tert-butylcyclohexyl group; or alternatively, a 2,6-dimethylcyclohexylgroup, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group,or a 2,6-di-tert-butylcyclohexyl group. In an aspect, R-heteroatomicligand structure provided herein, and/or any heteroatomic ligandtransition metal compound complex structure provided herein can be acyclopentyl group, a 2-methylcyclopentyl group, a cyclohexyl group, or a2-methylcyclohexyl group; alternatively, a cyclopentyl group or acyclohexyl group; or alternatively, a 2-methylcyclopentyl group or a2-methylcyclohexyl group.

In an aspect, R^(5s) can be a phenyl group or a substituted phenylgroup; alternatively, a phenyl group; or alternatively, a substitutedphenyl group. In some aspects, R^(5s) can be a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group or a 4-substituted phenylgroup; alternatively, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; alternatively, a 2-substituted phenyl group;alternatively, a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group. Inan aspect, one or more substituents of a multi-substituted phenyl grouputilized as R^(5s) can be the same or different; alternatively, all thesubstituents can be the same, or alternatively, all the substituents canbe different. Each substituent of a substituted phenyl group (general orspecific) independently can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a halogen or a hydrocarboxy group; alternatively, ahydrocarbyl group or a hydrocarboxy group; alternatively, a halogen;alternatively, a hydrocarbyl group; or alternatively, a hydrocarboxygroup. Substituent halogens, substituent hydrocarbyl groups (general andspecific), and substituent hydrocarboxy groups (general and specific)are independently described herein and these substituent groups can beutilized without limitation to further describe a substituted phenylgroup (general or specific) which can be utilized as R^(5s).

In a non-limiting aspect, R^(5s) can be a phenyl group, a 2-alkylphenylgroup, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively,a 2-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group. Alkyl substituent groups(general and specific) are independently described herein and thesealkyl substituent groups can be utilized, without limitation, to furtherdescribe any alkyl substituted phenyl group which can be utilized asR^(5s). Generally, the alkyl substituents of dialkylphenyl groups(general of specific) or trialkylphenyl groups (general or specific) canbe the same, or alternatively, the alkyl substituents can be different.In some non-limiting aspects, R^(5s) can be a phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, a 2-tert-butylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, or a2,4,6-trimethylphenyl group; alternatively, a phenyl group, a2-methylphenyl group, a 2,6-dimethylphenyl group, or a2,4,6-trimethylphenyl group.

Generally, L^(2s), of any heteroatomic ligand and/or any heteroatomicligand transition metal compound complex having an L^(2s) group, can bean organylene group; alternatively, an organylene group consisting ofinert functional groups; alternatively, a hydrocarbylene group; oralternatively, an alkylene group. In an aspect, the L^(2s) organylenegroup can be a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ organylene group.In an aspect, the L^(2s) organylene group consisting of inert functionalgroups can be a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ organylene groupconsisting of inert functional groups. In an aspect, the L^(2s) alkylenegroup can be a C₁ to C₂₀, C₁ to C₁₅, or a C₁ to C₁₀ alkylene group.

In an aspect, L^(2s) of any heteroatomic ligand and/or any heteroatomicligand transition metal compound complex having an L^(2s) group can be—(CR^(p)R^(p′))_(m)— where each R^(p) and R^(p′) can independently behydrogen, methyl, ethyl, propyl, isopropyl, or butyl groups and m can bean integer from 1 to 12. In some aspects, L^(2s) of any heteroatomicligand and/or any heteroatomic ligand transition metal compound complexhaving an L^(2s) group can be a methylene group (—CH₂—), aneth-1,2-ylene group (—CH₂CH₂—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), aprop-1,2-ylene group (—CH(CH₃)CH₂—), a prop-2,2-ylene group (—C(CH₃)₂—)group, a but-1,4-ylene group (—CH₂CH₂CH₂CH₂), or a2-methylprop-1,3-ylene group (—CH₂CH(CH₃)CH₂—); or alternatively amethylene group (—CH₂—), an eth-1,2-ylene group (—CH₂CH—), or aprop-1,2-ylene group (—CH(CH₃)CH₂).

In an aspect, L^(2s) of any heteroatomic ligand and/or any heteroatomicligand transition metal compound complex having an L^(2s) group, can be1,2-cyclohexylene, a substituted 1,2-cyclohexylene, 1,3-cyclohexylene, asubstituted 1,3-cyclohexylene, 1,4-cyclohexylene, a substituted1,4-cyclohexylene, 3,3′-bicyclohexylene, a substituted3,3′-bicyclohexylene, 4,4′-bicyclohexylene, a substituted4,4′-bicyclohexylene, bis(3-cyclohexylene)methane, a substitutedbis(3-cyclohexylene)methane, bis(4-cyclohexylene)methane, a substitutedbis(4-cyclohexylene)methane, 1,2-bis(3-cyclohexylene)ethane, asubstituted 1,2-bis(3-cyclohexylene)ethane,1,2-bis(4-cyclohexylene)ethane, a substituted1,2-bis(4-cyclohexylene)ethane, 1,2-bis(3-cyclohexylene)propane, asubstituted 1,2-bis(3-cyclohexylene)propane,1,2-bis(4-cyclohexylene)propane, a substituted1,2-bis(4-cyclohexylene)propane, 2,2-bis(3-cyclohexylene)-propane, asubstituted 2,2-bis(3-cyclohexylene)propane,2,2-bis(4-cyclohexylene)propane, or a substituted2,2-bis(4-cyclohexylene)propane. In some aspects, L^(2s) of anyheteroatomic ligand and/or any heteroatomic ligand transition metalcompound complex having an L^(2s) group can be a substituted1,2-cyclohexylene, a substituted 1,3-cyclohexylene, a substituted1,4-cyclohexylene, a substituted 3,3′-bicyclohexylene, a substituted4,4′-bicyclohexylene, a substituted bis(3-cyclohexylene)methane, asubstituted bis(4-cyclohexylene)methane, a substituted1,2-bis(3-cyclohexylene)ethane, a substituted1,2-bis(4-cyclohexylene)ethane, a substituted1,2-bis(3-cyclohexylene)propane, a substituted1,2-bis(4-cyclohexylene)-propane, a substituted2,2-bis(3-cyclohexylene)propane, or a substituted2,2-bis(4-cyclohexylene)propane. In an aspect, each substituent of asubstituted cyclohexylene, a substituted bis(cyclohexylene)methane, asubstituted bis(cyclohexylene)ethane, or a substituted1,2-bis(3-cyclohexylene)propane which can be utilized as L^(2s) can be ahydrocarbyl group. Substituent groups (general and specific) areindependently disclosed herein and can be utilized without limitation tofurther describe a substituted cyclohexylene (general or specific), asubstituted bis(cyclohexylene)methane (general or specific), asubstituted bis(cyclohexylene)ethane (general or specific), or asubstituted 1,2-bis(3-cyclohexylene)propane (general or specific) whichcan be utilized as L^(2s).

In an aspect, L^(2s) of any heteroatomic ligand and/or any heteroatomicligand transition metal compound complex having an L^(2s) group can be1,2-phenylene, a substituted 1,2-phenylene, 1,3-phenylene, a substituted1,3-phenylene, 1,4-phenylene, a substituted 1,4-phenylene,3,3′-biphenylene, a substituted 3,3′-biphenylene, 4,4′-biphenylene, asubstituted 4,4′-biphenylene, bis(3-phenylene)methane, a substitutedbis(3-phenylene)methane, bis(4-phenylene)methane, a substitutedbis(4-phenylene)methane, 1,2-bis(3-phenylene)ethane, a substituted1,2-bis(3-phenylene)ethane, 1,2-bis(4-phenylene)ethane, a substituted1,2-bis(4-phenylene)ethane, 1,2-bis(3-phenylene)propane, a substituted1,2-bis(3-phenylene)propane, 1,2-bis(4-phenylene)propane, a substituted1,2-bis(4-phenylene)propane, 2,2-bis(3-phenylene)propane, a substituted2,2-bis(3-phenylene)propane, 2,2-bis(4-phenylene)propane, or asubstituted 2,2-bis(4-phenylene)propane. In some aspects, L^(2s) of anyheteroatomic ligand and/or any heteroatomic ligand transition metalcompound complex having an L^(2s) group can be a substituted1,2-phenylene, a substituted 1,3-phenylene, a substituted 1,4-phenylene,a substituted 3,3′-biphenylene, a substituted 4,4′-biphenylene, asubstituted bis(3-phenylene)methane, a substitutedbis(4-phenylene)methane, a substituted 1,2-bis(3-phenylene)ethane, asubstituted 1,2-bis(4-phenylene)ethane, a substituted1,2-bis(3-phenylene)propane, a substituted 1,2-bis(4-phenylene)propane,a substituted 2,2-bis(3-phenylene)propane, or a substituted2,2-bis(4-phenylene)propane. In an aspect, each substituent of asubstituted phenylene (general or specific), a substituted biphenylene(general or specific), a substituted bis(phenylene)methane (general orspecific), a substituted bis(phenylene)ethane (general or specific),and/or a substituted bis(phenylene)propane (general or specific) whichcan be utilized as L^(2s) can be a hydrocarbyl group. Substituenthydrocarbyl groups (general and specific) are independently disclosedherein and can be utilized without limitation to further describe asubstituted phenylene (general or specific), a substituted biphenylene(general or specific), a substituted bis(phenylene)methane (general orspecific), a substituted bis(phenylene)ethane (general or specific),and/or a substituted bis(phenylene)propane (general or specific) whichcan be utilized as L^(2s).

Generally, L^(3s) and/or L^(4s), of any heteroatomic ligand and/or anyheteroatomic ligand transition metal compound complex having an L^(3s)and/or L^(4s) group, independently can be an organylene group;alternatively, an organylene group consisting of inert functionalgroups; alternatively, a hydrocarbylene group; alternatively, analkylene group. In an aspect, the L^(3s) and/or L^(4s) organylene groupindependently can be a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀ organylenegroup. In an aspect, the L^(3s) and/or L^(4s) organylene groupconsisting of inert functional groups independently can be a C₁ to C₂₀,a C₁ to C₁₅, or a C₁ to C₁₀ organylene group consisting of inertfunctional groups. In an aspect, the L^(3s) and/or L^(4s) hydrocarbylenegroup independently can be a C₁ to C₂₀, a C₁ to C₁₅, or a C₁ to C₁₀hydrocarbylene group. In an aspect, the L^(3s) and/or L^(4s) alkylenegroup independently can be a C₁ to C₂₀, C₁ to C₁₅, or a C₁ to C₁₀alkylene group.

In an aspect, L^(3s) and/or L^(4s) of any heteroatomic ligand structureand/or any heteroatomic ligand transition metal compound complex havingan L^(3s) and/or L^(4s) group independently can be —(CR^(p)R^(p′))_(m)—where each R^(p) and R^(p′) can independently be hydrogen, methyl,ethyl, propyl, isopropyl, or butyl groups and m can be an integer from 1to 12. In some aspects, L^(3s) and/or L^(4s) of any heteroatomic ligandstructure and/or any heteroatomic ligand transition metal compoundcomplex having an L^(3s) and/or L^(4s) group independently can be amethylene group (—CH₂—), an eth-1,2-ylene group (—CH₂CH₂—), anethen-1,2-ylene group (—CH═CH—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), aprop-1,2-ylene group (—CH(CH₃)CH₂—), a prop-2,2-ylene group (—C(CH₃)₂—),a 1-methylethen-1,2-ylene group (—C(CH₃)═CH—), a but-1,4-ylene group(—CH₂CH₂CH₂—CH₂—), a but-1,3-ylene group (—CH₂CH₂CH(CH₃)—), abut-2,3-ylene group (—CH(CH₃)CH(CH)—), a but-2-en-2,3-ylene group(—C(CH₃)C(CH₃)—), a 3-methylbut-1,3-ylene group (—CH₂CH₂C(CH₃)₂—), a1,2-cyclopentylene group, a 1,2-cyclohexylene group, or a phen-1,2-ylenegroup; alternatively, a methylene group (—CH₂—), an eth-1,2-ylene group(—CH₂CH₂—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), a prop-1,2-ylene group(—CH(CH₃)CH₂—), a prop-2,2-ylene group (—C(CH₃)₂—), a but-1,4-ylenegroup (—CH₂CH₂CH₂—CH₂—), a but-1,3-ylene group (—CH₂CH₂CH(CH₃)—), abut-2,3-ylene group (—CH(CH₃)CH(CH₃)—), a 1,2-cyclopentylene group, a1,2-cyclohexylene group, or a phen-1,2-ylene group; or alternatively, aneth-1,2-ylene group (—CH₂CH—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), aprop-1,2-ylene group (—CH(CH₃)CH₂—), a but-1,3-ylene group(—CH₂CH₂CH(CH₃)—), a but-2,3-ylene group (—CH(CH₃)CH(CH₃)—), a1,2-cyclopentylene group, a 1,2-cyclohexylene group, or a phen-1,2-ylenegroup.

Generally, the transition metal of the heteroatomic ligand transitionmetal compound complex or the transition metal compound, MX_(p) can beany transition metal atom. In an embodiment, the transition metal atomof the transition metal compound can comprise, or consist essentiallyof, a Group 3-12, a Group 4-10, a Group 6-9, or a Group 7-8 transitionmetal. In some embodiments, the transition metal atom of the transitionmetal compound can comprise, or consist essentially of, a Group 4transition metal; alternatively, a Group 5 transition metal;alternatively, a Group 6 transition metal; alternatively, a Group 7transition metal; alternatively, a Group 8 transition metal;alternatively, a Group 9 transition metal; or alternatively, a Group 10transition metal. In an embodiment, the transition metal atom of thetransition metal compound can comprise, or consist essentially of,titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium,platinum, copper, or zinc; alternatively, titanium, zirconium, vanadium,chromium, molybdenum, tungsten, iron, cobalt, nickel, palladium, orplatinum; alternatively, chromium, iron, cobalt, or nickel;alternatively, titanium, zirconium, or hafnium; alternatively, vanadiumor niobium; alternatively, chromium, molybdenum, or tungsten;alternatively, iron or cobalt; or alternatively, nickel, palladium,platinum, copper, or zinc. In other embodiments, the metal salt cancomprise titanium; alternatively, zirconium; alternatively, hafnium;alternatively, vanadium; alternatively, niobium; alternatively,tantalum; alternatively, chromium; alternatively, molybdenum;alternatively, tungsten; alternatively, manganese; alternatively, iron;alternatively, cobalt; alternatively, nickel; alternatively, palladium;alternatively, platinum; alternatively, copper; or alternatively, zinc.Generally, the transition metal atom of the heteroatomic ligandtransition metal compound complex or the transition metal compound,MX_(p), can have any positive oxidation state available to thetransition metal atom. In an embodiment, the transition metal atom canhave an oxidation state of from +2 to +6; alternatively, from +2 to +4;or alternatively, from +2 to +3. In some embodiments, the transitionmetal atom of the transition metal compound, MX_(p), can have anoxidation state of +1; alternatively, +2; alternatively, +3; oralternatively, +4.

In an aspect, the transition metal of the heteroatomic ligand transitionmetal compound complex or the transition metal compound, MX_(p) can bechromium, Cr. The chromium compound or the chromium compound of theheteroatomic ligand chromium compound complexes described herein canhave formula CrX_(p) where X represents a monoanionic ligand, and prepresents the number of monoanionic ligands (and the oxidation state ofthe chromium in the chromium compound. The monoanionic ligand (X), and pare independent elements of the chromium compound or the chromiumcompound of the heteroatomic ligand chromium compound complexesdescribed herein and are independently described herein. The independentdescriptions of the monoanionic ligand (X), and p can be utilizedwithout limitation, and in any combination, to further describe thechromium compound or the chromium compound of the heteroatomic ligandchromium compound complexes described herein. The chromium atom of thechromium compound (CrX_(p)) can have any positive oxidation stateavailable to a chromium atom. In an aspect, the chromium atom can havean oxidation state of from +2 to +6; alternatively, from +2 to +4; oralternatively, from +2 to +3. In some aspects, the chromium atom of thechromium compound (CrX_(p)) can have an oxidation state of +1;alternatively, +2; alternatively, +3; or alternatively, +4.

The monoanion (X) of the transition metal compound can be any monoanion.In an aspect, the monoanion (X) can be a halide, a carboxylate, aβ-diketonate, a hydrocarboxide, a nitrate, or a chlorate. In someaspects, the monoanion (X) can be a halide, a carboxylate, aβ-diketonate, or a hydrocarboxide. In any aspect, the hydrocarboxide canbe an alkoxide, an aryloxide, or an aralkoxide. Generally,hydrocarboxide (and subdivisions of hydrocarboxide) are the anionanalogues of the hydrocarboxy group. In other aspects, the monoanion (X)can be a halide, a carboxylate, a β-diketonate, or an alkoxide; oralternatively, a halide or a β-diketonate. In other aspects, themonoanion (X) can be a halide; alternatively, a carboxylate;alternatively, a β-diketonate; alternatively, a hydrocarboxide;alternatively, an alkoxide; or alternatively, an aryloxide. Generally,when the heteroatomic ligand of the heteroatomic ligand transition metalcompound complex is a neutral heteroatomic ligand the number ofmonoanions (p) can equal the oxidation state of the transition metalatom. When the heteroatomic ligand of the heteroatomic ligand transitionmetal compound complex is an anionic heteroatomic ligand the number ofmonoanions (p) can equal one less than the oxidation state of thetransition metal atom. In an aspect, the number of monoanions can befrom 2 to 6; alternatively, from 2 to 4; alternatively, from 2 to 3;alternatively, 1; alternatively, 2; alternatively, 3; or alternatively,4.

Generally, each halide of the transition metal compound independentlycan be fluorine, chlorine, bromine, or iodine; or alternatively,chlorine, bromine, or iodine. In an aspect, each halide monoanion of thetransition metal compound can be chlorine; alternatively, bromine; oralternatively, iodine.

Generally, each carboxylate of the transition metal compoundindependently can be a C₁ to C₂₀ carboxylate; or alternatively, a C₁ toC₁₀ carboxylate. In an aspect, each carboxylate of the transition metalcompound independently can be acetate, a propionate, a butyrate, apentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, adecanoate, an undecanoate, or a dodecanoate; or alternatively, apentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, adecanoate, an undecanoate, or a dodecanoate. In some aspects, eachcarboxylate of the transition metal compound independently can beacetate, propionate, n-butyrate, valerate (n-pentanoate),neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate(n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate),n-undecanoate, or laurate (n-dodecanoate); alternatively, valerate(n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate,caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate(n-decanoate), n-undecanoate, or laurate (n-dodecanoate); alternatively,capronate (n-hexanoate); alternatively, n-heptanoate; alternatively,caprylate (n-octanoate); or alternatively, 2-ethylhexanoate. In someaspects, the carboxylate of the transition metal compound can betriflate (trifluoroacetate).

Generally, each β-diketonate of the transition metal compoundindependently can be any C₁ to C₂₀ a β-diketonate; or alternatively, anyC₁ to C₁₀ β-diketonate. In an aspect, each β-diketonate of the chromiumcompound independently can be acetylacetonate (i.e.,2,4-pentanedionate), hexafluoroacetylacetonate (i.e.,1,1,1,5,5,5-hexafluoro-2,4-pentanedionate), or benzoylacetonate);alternatively, acetylacetonate; alternatively,hexafluoroacetylacetonate; or alternatively, benzoylacetonate.

Generally, each hydrocarboxide of the transition metal compoundindependently can be any C₁ to C₂₀ hydrocarboxide; or alternatively, anyC₁ to C₂₀ hydrocarboxide. In an aspect, each hydrocarboxide of thetransition metal compound independently can be a C₁ to C₂₀ alkoxide;alternatively, a C₁ to C₁₀ alkoxide; alternatively, a C₆ to C₂₀aryloxide; or alternatively, a C₆ to C₁₀ aryloxide. In an aspect, eachalkoxide of the transition metal compound independently can bemethoxide, ethoxide, a propoxide, or a butoxide; alternatively,methoxide, ethoxide, isopropoxide, or tert-butoxide; alternatively,methoxide; alternatively, an ethoxide; alternatively, an iso-propoxide;or alternatively, a tert-butoxide. In an aspect, the aryloxide can bephenoxide.

In some aspects, the transition metal of the transition metal compoundand/or the transition metal compound of the heteroatomic ligandtransition metal compound complex can be chromium. When the transitionmetal is chromium the transition metal compound can be referred to as achromium compound and the heteroatomic ligand transition metal compoundcomplex of the catalyst systems described herein can be referred to as aheteroatomic ligand chromium compound complex. In an aspect where thetransition metal is chromium, the heteroatomic ligand chromium compoundcomplex of the catalyst system can be comprise an N²-phosphinylformamidine chromium compound complex, an N²-phosphinyl amidine chromiumcompound complex, an N²-phosphinyl guanidine chromium compound complex,or any combination thereof; alternatively, an N²-phosphinyl formamidinechromium compound complex; alternatively, an N²-phosphinyl amidinechromium compound complex; or alternatively, an N²-phosphinyl guanidinechromium compound complex.

In an aspect, the N²-phosphinyl formamidine chromium compound complexutilized in the catalyst systems described herein can have StructureNPFCr1. In an aspect, the N²-phosphinyl amidine chromium compoundcomplex can have Structure NPACr1. In an aspect, the N²-phosphinylguanidine chromium compound complex can have Structure GuCr1, GuCr2,GuCr3, GuCr4, or GuCr5; alternatively, Structure GuCr1; alternatively,Structure GuCr2; alternatively, Structure GuCr3; alternatively,Structure GuCr4; or alternatively, Structure GuCr5. In an aspect, theheterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplex can have Structure HCPACr1.

Descriptions and options for R¹, R², R^(2a), R^(2b), R³, R⁴, R⁵, L¹²,L²², L²³, X, p, Q, and q are independently described herein and theseindependent descriptions and options can be utilized without limitationand in any combination to further describe the N²-phosphinyl formamidinechromium compound complexes, the N²-phosphinyl amidine chromium compoundcomplexes, the N²-phosphinyl guanidine chromium compound complexes, andthe heterocyclic 2-[(phosphinyl)aminyl]imine transition metal compoundcomplexes contemplated by Structures NPFCr1, Structure NPACr1, StructureGuCr1, Structure GuCr2, Structure GuCr3, Structure GuCr4, StructureGuCr5, and/or Structure HCPACr1.

In another aspect where the transition metal is chromium, the transitionmetal compound can have any of one of the formulas

Descriptions and options for R^(1s), R^(2s), X^(1s), X^(2s), L^(1s), m,n, X, and p, are independently described herein and these independentdescriptions and options can be utilized without limitation and in anycombination to further describe the heteroatomic ligand chromiumcompound complexes having the depicted formulas.

In further aspects where the transition metal is chromium, thetransition metal compound can have Structure PNPCr1, Structure PNPCr2,Structure NRNCr1, Structure PRPCr1, Structure SRNCr1, Structure PRNCr1,and/or Structure NRPCr1.

Descriptions and options for R^(5s), R^(11s), R^(12s), R^(13s), R^(14s),L^(2s), L^(3s), L^(4s), X, and p are independently described herein andthese independent descriptions and options can be utilized withoutlimitation and in any combination to further describe the heteroatomicligand chromium compound complexes having Structure PNPCr1, StructurePNPCr2, Structure NRNCr1, Structure PRPCr1, Structure SRNCr1, StructurePRNCr1, and/or Structure NRPCr1.

In some non-limiting aspects, the chromium compound and/or the chromiumcompound of the heteroatomic ligand chromium compound complex cancomprise, can consist essentially of, or consist of, a chromium(II)halide, a chromium(II) carboxylate, or a chromium(II) β-diketonate; oralternatively, a chromium(III) halide, a chromium(III) carboxylate, or achromium(III) β-diketonate. In other non-limiting aspects, the chromiumcompound and/or the chromium compound of the heteroatomic ligandchromium compound complex can comprise, can consist essentially of orconsist of, a chromium(II) halide; alternatively, a chromium(III)halide; alternatively, a chromium (II) carboxylate; alternatively, achromium(III) carboxylate; alternatively, a chromium(II) β-diketonate;or alternatively, a chromium(III) β-diketonate. Halides, carboxylates,β-diketonates are independently described herein and these halides,carboxylates, β-diketonate and these independently described halides,carboxylates, β-diketonates can be utilized without limitation and inany combination to further described the chromium compound and/or thechromium compound of the heteroatomic ligand chromium compound complex.In further non-limiting aspects, the chromium compound and/or thechromium compound of the heteroatomic ligand chromium compound complexcan comprise, can consist essentially of, or consist of, chromium(II)chloride, chromium(III) chloride, chromium(II) fluoride, chromium(III)fluoride, chromium(II) bromide, chromium(III) bromide, chromium(II)iodide, chromium(III) iodide, chromium(II) acetate, chromium(III)acetate, chromium(II) 2-ethylhexanoate, chromium(III) 2-ethylhexanoate,chromium(II) triflate, chromium(III) triflate, chromium(II) nitrate,chromium(III) nitrate, chromium(II) acetylacetonate, chromium(III)acetylacetonate, chromium(II) hexafluoracetylacetonate, chromium(III)hexafluoracetylacetonate, chromium(III) benzoylacetonate, orchromium(III) benzoylacetonate; alternatively, chromium(III) chloride,chromium(III) fluoride, chromium(III) bromide, chromium(III) iodide,chromium(III) chloride (THF) complex, chromium(III) acetate,chromium(III) 2-ethylhexanoate, chromium(III) triflate, chromium(III)nitrate, chromium(III) acetylacetonate, chromium(III)hexafluoracetylacetonate, or chromium(III) benzoylacetonate;alternatively, chromium(III) chloride, or chromium(III) acetylacetonate;alternatively, chromium(III) chloride; or alternatively, chromium(III)acetylacetonate.

In a non-limiting aspect, the heteroatomic ligand chromium compoundcomplex can be selected from any one or more of a heteroatomic ligandchromium compound complex having i) Structure NPFCr1 where R¹ is2,6-dimethylphenyl, R³ is H, R⁴ and R⁵ are isopropyl, and X is chlorine;R¹ is 2,6-dimethylphenyl. R³ is H, R⁴ and R⁵ are phenyl, and X ischlorine; R¹ is 2,6-dimethylphenyl, R³ is H, R⁴ and R⁵ are4-methoxyphenyl, and X is chlorine; R¹ is 2,4,6-trimethylphenyl, R³ isH, R⁴ and R⁵ are isopropyl, and X is chlorine; R¹ is2,4,6-trimethylphenyl, R³ is H, R⁴ and R⁵ are phenyl, and X is chlorine;and R¹ is 2,4,6-trimethylphenyl, R³ is H, R⁴ and R⁵ are 4-methoxyphenyl,and X is chlorine; ii) Structure NPACr1 where R¹ is 2,6-dimethylphenyl,R² is phenyl, R³ is H, R⁴ and R⁵ are isopropyl, and X is chlorine; R¹ is2,4,6-trimethylphenyl, R² is phenyl, R³ is H, R⁴ and R⁵ are isopropyl,and X is chlorine; R¹ is 2,6-dimethylphenyl, R² is phenyl, R³ is H, R⁴and R⁵ are phenyl, and X is chlorine; R¹ is 2,4,6-trimethylphenyl, R² isphenyl, R³ is H, R⁴ and R⁵ are phenyl, and X is chlorine; R¹ is2,6-dimethylphenyl, R² is 4-methylbenzyl, R³ is H, R⁴ and R⁵ are phenyl,and X is chlorine; R¹ is 2,6-dimethylphenyl, R² is phenyl, R³ is H, R⁴and R⁵ are 4-methoxyphenyl, and X is chlorine; R¹ is 2,6-dimethylphenyl,R² is 4-t-butylphenyl, R³ is H, R⁴ and R⁵ are methyl, and X is chlorine;R¹ is 2,4,6-trimethylphenyl, R² is 4-t-butylphenyl, R³ is H, R⁴ and R⁵are methyl, and X is chlorine; R¹ is 2,4,6-trimethylphenyl, R² is4-methylbenzyl, R³ is H, R⁴ and R⁵ are isopropyl, and X is chlorine; R¹is 2,4,6-trimethylphenyl, R² is 4-methylbenzyl, R³ is H, R⁴ and R⁵ arephenyl, and X is chlorine; R¹ is 3,5-dimethylphenyl, R² is phenyl, R³ isH, R⁴ and R⁵ are isopropyl, and X is chlorine; R¹ is2,4,6-trimethylphenyl, R² is 4-methylbenzyl, R³ is H, R⁴ and R⁵ are4-methoxyphenyl, and X is chlorine; R¹ is 2,4,6-trimethylphenyl, R² is4-methylbenzyl, R³ is H, R⁴ is t-butyl, R⁴ is phenyl, and X is chlorine;R⁵ is 2,4,6-trimethylphenyl, R² is 4-methylbenzyl, R³ is H, R⁴ ismethyl, R⁵ is phenyl, and X is chlorine; R¹ and R² are joined to formaprop-1,3-ylene group, R³ is H, R⁴ and R⁵ are isopropyl, and X ischlorine; R¹ and R² are joined to form a but-1,4-ylene group, R³ is H,R⁴ and R⁵ are isopropyl, and X is chlorine; R¹ is 2,4,6-trimethylphenyl,R² is 4-methylbenzyl, R³ is H, R⁴ and R⁵ are joined to form abut-1,4-ylene group, and X is chlorine; R¹ is 2,4,6-trimethylphenyl, R²is 4-methylbenzyl, R³ is H, R⁴ and R⁵ are joined to form a2,2′-dimethylbiphenylene group, and X is chlorine; iii) Structure GUCr1where R¹ is 2-methylphenyl, R^(2a) is 2-methylphenyl, R^(2b) is H, R³ isH, R⁴ and R⁵ are isopropyl, and X is chlorine; R₁ is 2,6-dimethylphenyl,R^(2a) is phenyl, R^(2b) is H, R³ is H, R⁴ and R⁵ are isopropyl, and Xis chlorine; R¹ is 2,6-dimethylphenyl, R^(2a) is phenyl, R^(2b) is H, R³is H, R⁴ and R⁵ are phenyl, and X is chlorine; R¹ is 2,6-dimethylphenyl,R^(2a) and R^(2b) are phenyl, R³ is H, R⁴ and R⁵ are isopropyl, and X ischlorine; iv) Structure GUCr4 where L¹² is prop-1,3-ylene, L²³ isprop-1,3-ylene, R⁴ and R⁵ are isopropyl, and X is chlorine; L¹² isprop-1,3-ylene, L²³ is prop-1,3-ylene, R⁴ and R⁵ are cyclopentyl, and Xis chlorine; L¹² is prop-1,3-ylene, L²³ is prop-1,3-ylene, R⁴ and R⁵ arecyclohexyl, and X is chlorine; L¹² is prop-1,3-ylene, L²³ isprop-1,3-ylene, R⁴ and R⁵ are phenyl, and X is chlorine; L¹² isbut-1,3-ylene, L²³ is prop-1,3-ylene, R⁴ and R⁵ are isopropyl, and X ischlorine; L¹² is but-1,3-ylene, L²³ is prop-1,3-ylene, R⁴ and R⁵ arecyclopentyl, and X is chlorine; L¹² is but-1,3-ylene, L²³ isbut-1,3-ylene, R⁴ and R⁵ are isopropyl, and X is chlorine; L¹² isbut-1,3-ylene, L²³ is but-1,3-ylene, R⁴ and R⁵ are phenyl, and X ischlorine; L¹² is ethen-1,2-ylene, L²³ is prop-1,3-ylene, R⁴ and R⁵ areisopropyl, and X is chlorine; L¹² is ethen-1,2-ylene, L²³ isprop-1,3-ylene, R⁴ and R⁵ are cyclopentyl, and X is chlorine; L¹² isethen-1,2-ylene, L²³ is prop-1,3-ylene, R⁴ and R⁵ are cyclohexyl, and Xis chlorine; L¹² is phen-1,2-ylene, L²³ is eth-1,2-ylene, R⁴ and R⁵ areisopropyl, and X is chlorine; and v) Structure HCPACr2 where T issulfur, L¹² is ethen-1,2-ylene, R³ is H, R⁴ and R⁵ are isopropyl, and Xis chlorine; and T is sulfur, L¹² is phen-1,2-ylene, R³ is H, R⁴ and R⁵are isopropyl, and X is chlorine.

In another non-limiting aspect, the heteroatomic ligands for theheteroatomic ligand chromium compound complexes can be selected from anyone or more of HL 1, HL 2, HL 3, HL 4, HL 5, HL 6, HL 7, HL 7, and HL 9.In other non-limiting aspects, the heteroatomic ligand chromium compoundcomplexes can be selected from a diphosphino amine chromium compoundcomplex of any one or more of HLCr 1, HLCr 2, HLCr 3, HLCr 4, HLCr 5,HLCr 6, HLCr 7, HLCr 8, and HLCr 9. In other non-limiting aspects, theheteroatomic ligand chromium compound complex can be selected from thechromium(III) chloride or chromium(III) acetylacetonate complex of adiphosphino amine chromium compound complex of any one or more of HLCr1, HLCr 2, HLCr 3, HLCr 4, HLCr 5, HLCr 6, HLCr 7, HLCr 8, and HLCr 9.

While not shown in all of the transition metal compound names andformulas, heteroatomic ligand transition metal compound complex formulasand structures, or the heteroatomic ligand chromium compound complexformulas and structures, one of ordinary skill in the art will recognizethat a neutral ligand can be associated with the transition metalcompounds, heteroatomic ligand transition metal compound complexes,and/or the heteroatomic ligand chromium compound complexesdescribed/depicted herein which do not explicitly disclose/depict aneutral ligand. Additionally it should be understood that while some thetransition metal compounds, heteroatomic ligand transition metalcompound complexes, and/or the heteroatomic ligand chromium compoundcomplexes described/depicted/provided herein do not formally show thepresence of a neutral ligand, the transition metal compounds,heteroatomic ligand transition metal compound complexes, and/or theheteroatomic ligand chromium compound complexes having neural ligands(e.g., nitriles and ethers, among others) are implicitly and fullycontemplated as potential the transition metal compounds, heteroatomicligand transition metal compound complexes, and/or the heteroatomicligand chromium compound complexes that can be utilized in the catalystsystem used in aspects of the herein described inventions.

Generally, the neutral ligand of any transition metal compound,heteroatomic ligand transition metal compound complex, or heteroatomicligand chromium compound complex, when present, independently can be anyneutral ligand that forms an isolatable compound with the transitionmetal compound, heteroatomic ligand transition metal compound complex,or heteroatomic ligand chromium compound complex. In an aspect, eachneutral ligand independently can be a nitrile or an ether;alternatively, a nitrile; or alternatively, an ether. The number ofneutral ligands, q, can be any number that forms an isolatable compoundwith the transition metal compound, heteroatomic ligand transition metalcompound complex, or heteroatomic ligand chromium compound complex. Inan aspect, the number of neutral ligands can be from 0 to 6;alternatively, 0 to 3; alternatively, 0; alternatively, 1;alternatively, 2; alternatively, 3; or alternatively, 4.

Generally, each nitrile ligand independently can be a C₂ to C₂₀ nitrile;or alternatively, a C₂ to C₁₀ nitrile. In an aspect, each nitrile ligandindependently can be a C₂ to C₂₀ aliphatic nitrile, a C₇ to C₂₀ aromaticnitrile, a C₈ to C₂₀ aralkane nitrile, or any combination thereof;alternatively, a C₂ to C₂₀ aliphatic nitrile; alternatively, a C₇ to C₂₀aromatic nitrile; or alternatively, a C₈ to C₂₀ aralkane nitrile. Insome aspects, each nitrile ligand independently can be a C₂ to C₁₀aliphatic nitrile, a C₇ to C₁₀ aromatic nitrile, a C₈ to C₁₀ aralkanenitrile, or any combination thereof; alternatively, a C₁ to C₁₀aliphatic nitrile; alternatively, a C₇ to C₁₀ aromatic nitrile; oralternatively, a C₈ to C₁₀ aralkane nitrile. In an aspect, eachaliphatic nitrile independently can be acetonitrile, propionitrile, abutyronitrile, benzonitrile, or any combination thereof; alternatively,acetonitrile; alternatively, propionitrile; alternatively, abutyronitrile; or alternatively, benzonitrile.

Generally, each ether ligand independently can be a C₂ to C₄₀ ether;alternatively, a C₂ to C₃₀ ether; or alternatively, a C₂ to C₂₀ ether.In an aspect, each ether ligand independently can be a C₂ to C₄₀aliphatic ether, a C₃ to C₄₀ aliphatic cyclic ether, a C₄ to C₄₀aromatic cyclic ether; alternatively, a C₂ to C₄₀ aliphatic acyclicether or a C₃ to C₄₀ aliphatic cyclic ether; alternatively, a C₂ to C₄₀aliphatic acyclic ether; alternatively, a C₃ to C₄₀ aliphatic cyclicether; or alternatively, a C₄ to C₄₀ aromatic cyclic ether. In someaspects, each ether ligand independently can be a C₂ to C₃₀ aliphaticether, a C₃ to C₃₀ aliphatic cyclic ether, a C₄ to C₃₀ aromatic cyclicether; alternatively, a C₂ to C₃₀ aliphatic acyclic ether or a C₃ to C₃₀aliphatic cyclic ether; alternatively, a C₂ to C₃₀ aliphatic acyclicether; alternatively, a C₃ to C₃₀ aliphatic cyclic ether; oralternatively, a C₄ to C₃₀ aromatic cyclic ether. In other aspects, eachether ligand independently can be a C₂ to C₂₀ aliphatic ether, a C₃ toC₂₀ aliphatic cyclic ether, a C₄ to C₂₀ aromatic cyclic ether;alternatively, a C₂ to C₂₀ aliphatic acyclic ether or a C₃ to C₂₀aliphatic cyclic ether; alternatively, a C₂ to C₂₀ aliphatic acyclicether; alternatively, a C₃ to C₂₀ aliphatic cyclic ether; oralternatively, a C₄ to C₂₀ aromatic cyclic ether. In some aspects, eachether ligand independently can be dimethyl ether, diethyl ether, adipropyl ether, a dibutyl ether, methyl ethyl ether, a methyl propylether, a methyl butyl ether, tetrahydrofuran, a dihydrofuran,1,3-dioxolane, tetrahydropyran, a dihydropyran, a pyran, a dioxane,furan, benzofuran, isobenzofuran, dibenzofuran, diphenyl ether, aditolyl ether, or any combination thereof; alternatively, dimethylether, diethyl ether, a dipropyl ether, a dibutyl ether, methyl ethylether, a methyl propyl ether, a methyl butyl ether, or any combinationthereof; tetrahydrofuran, a dihydrofuran, 1,3-dioxolane,tetrahydropyran, a dihydropyran, a pyran, a dioxane, or any combinationthereof; furan, benzofuran, isobenzofuran, dibenzofuran, or anycombination thereof; diphenyl ether, a ditolyl ether, or any combinationthereof; alternatively, dimethyl ether; alternatively, diethyl ether;alternatively, a dipropyl ether; alternatively, a dibutyl ether;alternatively, methyl ethyl ether; alternatively, a methyl propyl ether;alternatively, a methyl butyl ether; alternatively, tetrahydrofuran;alternatively, a dihydrofuran; alternatively, 1,3-dioxolane;alternatively, tetrahydropyran; alternatively, a dihydropyran;alternatively, a pyran; alternatively, a dioxane; alternatively, furan;alternatively, benzofuran; alternatively, isobenzofuran; alternatively,dibenzofuran; alternatively, diphenyl ether; or alternatively, a ditolylether.

Generally, the organoaluminum compound utilized in the catalyst systemsdisclosed herein can be any organoaluminum compound which in conjunctionwith the heteroatomic ligand transition metal compound complex (or thetransition metal compound and heteroatomic ligand) can catalyze theformation of an oligomer product. In an aspect, the organoaluminumcompound can comprise, consist essentially of, or be an aluminoxane, analkylaluminum compound, or any combination thereof; alternatively, analuminoxane; or alternatively, an alkylaluminum compound. In an aspect,the alkylaluminum compound comprise, consist essentially of, or be atrialkylaluminum, an alkylaluminum halide, an alkylaluminum alkoxide, orany combination thereof. In some aspects, the alkylaluminum compoundcomprise, consist essentially of, or be a trialkylaluminum, analkylaluminum halide, or any combination thereof; alternatively, atrialkylaluminum, an alkylaluminum alkoxide, or any combination thereof;or alternatively, a trialkylaluminum. In other aspects, thealkylaluminum compound can be a trialkylaluminum; alternatively, analkylaluminum halide; or alternatively, an alkylaluminum alkoxide. In anaspect, the aluminoxane utilized in the catalyst systems which areutilized in the processes and systems comprise, consist essentially of,or be any aluminoxane which in conjunction with the heteroatomic ligandtransition metal compound complex (or the transition metal compound andheteroatomic ligand), can catalyze the formation of an oligomer product.In a non-limiting aspect, the aluminoxane can have a repeating unitcharacterized by the Formula I:

wherein R′ is a linear or branched alkyl group. Alkyl groups of thealuminoxanes and alkylaluminum compounds are independently describedherein and can be utilized without limitation to further describe thealuminoxanes having Formula I and/or the alkylaluminum compounds.Generally, n of Formula I can be greater than 1; or alternatively,greater than 2. In an aspect, n can range from 2 to 15; oralternatively, range from 3 to 10.

In an aspect, each alkyl group of an aluminoxane and/or alkylaluminumcompound independently can be a C₁ to C₂₀ alkyl group; alternatively, aC₁ to C₁₀ alkyl group; or alternatively, a C₁ to C₆ alkyl group. In anaspect, each alkyl group of an aluminoxane and/or alkylaluminum compounda methyl group, an ethyl group, a propyl group, a butyl group, a pentylgroup, a hexyl group, a heptyl group, or an octyl group; alternatively,a methyl group, a ethyl group, a butyl group, a hexyl group, or an octylgroup. In some aspects, each alkyl group of an aluminoxane and/oralkylaluminum compound can be a methyl group, an ethyl group, ann-propyl group, an n-butyl group, an iso-butyl group, an n-hexyl group,or an n-octyl group; alternatively, a methyl group, an ethyl group, ann-butyl group, or an iso-butyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an n-propyl group;alternatively, an n-butyl group; alternatively, an iso-butyl group;alternatively, an n-hexyl group; or alternatively, an n-octyl group.

In a non-limiting aspect, the aluminoxane comprise, consist essentiallyof, or be methylaluminoxane (MAO), ethylaluminoxane, modifiedmethylaluminoxane (MMAO), n-propylaluminoxane, iso-propyl-aluminoxane,n-butylaluminoxane, sec-butylaluminoxane, iso-butylaluminoxane,t-butylaluminoxane, 1-pentylaluminoxane, 2-entylaluminoxane,3-pentyl-aluminoxane, iso-pentyl-aluminoxane, neopentylaluminoxane, ormixtures thereof. In some non-limiting aspects, the aluminoxanecomprise, or consist essentially of, or be methylaluminoxane (MAO),modified methylaluminoxane (MMAO), isobutyl aluminoxane, t-butylaluminoxane, or mixtures thereof. In other non-limiting aspects, thealuminoxane can be, comprise, or consist essentially of,methylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively,modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane;alternatively, iso-propyl-aluminoxane; alternatively,n-butylaluminoxane; alternatively, sec-butylaluminoxane; alternatively,iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively,1-pentyl-aluminoxane; alternatively, 2-pentylaluminoxane; alternatively,3-pentyl-aluminoxane; alternatively, iso-pentyl-aluminoxane; oralternatively, neopentylaluminoxane.

Various aspects described herein refer to non-hydrogen substituents suchas halogen (or halo, halide), hydrocarbyl, hydrocarboxy, alkyl, and/oralkoxy substituents. In an embodiment, each non-hydrogen substituent ofany aspect calling for a substituent can be a halogen, a hydrocarbylgroup, or a hydrocarboxy group; alternatively, a halogen or ahydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Each hydrocarbyl substituentindependently can be a C₁ to C₁₀ hydrocarbyl group; or alternatively, aC₁ to C₅ hydrocarbyl group. Each hydrocarboxy substituent independentlycan be a C₁ to C₁₀ hydrocarboxy group; or alternatively, a C₁ to C₅hydrocarboxy group. Each halide substituent independently can be afluoride, chloride, bromide, or iodide; alternatively, a fluoride orchloride; alternatively, a fluoride; alternatively, a chloride;alternatively, a bromide; or alternatively, an iodide.

In an aspect, any hydrocarbyl substituent independently can be an alkylgroup, an aryl group, or an aralkyl group; alternatively, an alkylgroup; alternatively, an aryl group; or alternatively, an aralkyl group.In an aspect, any alkyl substituent independently can be a methyl group,an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentylgroup, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butyl group, atert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butyl group,or a neo-pentyl group; alternatively, a methyl group, an ethyl group, anisopropyl group, a tert-butyl group, or a neo-pentyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an isopropyl group; alternatively, a tert-butyl group; oralternatively, a neo-pentyl group. In an aspect, any aryl substituentindependently can be phenyl group, a tolyl group, a xylyl group, or a2,4,6-trimethylphenyl group; alternatively, a phenyl group;alternatively, a tolyl group, alternatively, a xylyl group; oralternatively, a 2,4,6-trimethylphenyl group. In an aspect, any aralkylsubstituent independently can be benzyl group or an ethylphenyl group(2-phenyleth-1-yl or 1-phenyleth-1-yl); alternatively, a benzyl group;alternatively, an ethylphenyl group; alternatively, a 2-phenyleth-1-ylgroup; or alternatively, a 1-phenyleth-1-yl group.

In an aspect, any hydrocarboxy substituent independently can be analkoxy group, an aryloxy group, or an aralkoxy group; alternatively, analkoxy group; alternatively, an aryloxy group, or an aralkoxy group. Inan aspect, any alkoxy substituent independently can be a methoxy group,an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxygroup, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, ann-pentoxy group, a 2-pentoxy group, a 3-pentoxy group, a2-methyl-1-butoxy group, a tert-pentoxy group, a 3-methyl-1-butoxygroup, a 3-methyl-2-butoxy group, or a neo-pentoxy group; alternatively,a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxygroup, or a neo-pentoxy group; alternatively, a methoxy group;alternatively, an ethoxy group; alternatively, an isopropoxy group;alternatively, a tert-butoxy group; or alternatively, a neo-pentoxygroup. In an aspect, any aryloxy substituent independently can bephenoxy group, a toloxy group, a xyloxy group, or a2,4,6-trimethylphenoxy group; alternatively, a phenoxy group;alternatively, a toloxy group, alternatively, a xyloxy group; oralternatively, a 2,4,6-trimethylphenoxy group. In an aspect, anyaralkoxy substituent independently can be benzoxy group.

Generally, the heat exchange medium (also referred to as the first heatexchange medium) can be any fluid capable of maintaining the desiredreaction mixture temperature through heat exchange contact in the firstheat exchanger. In any process, reaction system, or heat exchange systemdescribed herein, the heat exchange medium can have a boiling point at 1atmosphere (101.3 kPa) greater than a reaction mixture temperature (oraverage reaction mixture temperature) on the first heat exchange surfacefirst side (e.g. first heat exchange surface first side 113) and canhave a boiling point at the pressure on the first heat exchange surfacesecond side (e.g. first heat exchange surface second side 114) less thanthe reaction mixture temperature (or average reaction mixturetemperature) on the first heat exchange surface first side (e.g. firstheat exchange surface first side 113). In any process, reaction system,or heat exchange system described herein, the minimum first heatexchange medium boiling point at 1 atmosphere (101.3 kPa) can be 40, 50,60, or 70° C.; alternatively or additionally, the maximum first heatexchange medium boiling point at 1 atmosphere (101.3 kPa) can be 150,140, 130, 120, or 110° C. The first heat exchange medium boiling pointat 1 atmosphere (101.3 kPa) can range from any boiling point at 1atmosphere (101.3 kPa) minimum temperature disclosed herein to anyboiling point at 1 atmosphere (101.3 kPa) maximum temperature disclosedherein. Non-limiting ranges for the first heat exchange medium boilingpoint at 1 atmosphere (101.3 kPa) can include a boiling point at 1atmosphere (101.3 kPa) in a range from 40 to 150° C., 50 to 140° C., 60to 130° C., 70 to 120° C., or 70 to 110° C. Other suitable ranges forthe first heat exchange medium boiling point at 1 atmosphere (101.3 kPa)are readily apparent from the present disclosure.

For any process, reaction system, or heat exchange system describedherein, the first heat exchange medium can be an organic heat exchangemedium or an inorganic heat exchange medium; alternatively, an organicheat exchange medium; or alternatively, an inorganic heat exchangemedium. Organic heat exchange mediums which can be utilized as the firstheat exchange medium can comprise C₆ to C₈ hydrocarbons; alternatively,C₆ to C₈ aliphatic hydrocarbons; or alternatively C₆ to C₈ saturatedhydrocarbons. Inorganic heat exchange mediums which can be utilized asthe first heat exchange medium can include or comprise water. Dependingupon the specific first heat exchange medium utilized, the heat exchangemedium can include additives such as corrosion inhibitors, oxygenscavengers, emulsifying agents, dispersants, antifoaming agents,neutralizing agents, filming agents, deposit control agents, among otheradditives.

For any process, reaction system, or heat exchange system describedherein, the second heat exchange medium can be any fluid capable ofmaintaining the desired first heat exchange medium temperature throughheat exchange contact in the second heat exchanger (i.e., second heatexchanger 211) or with the second heat exchange surface (i.e., secondheat exchange surface 212). In an aspect, the second heat exchangemedium on the second heat exchange surface second side (i.e., secondheat exchange surface second side 214) can have a boiling point greaterthan boiling point of the first heat exchange medium at the pressure onthe first heat exchange surface second side/second heat exchange surfacefirst side (i.e., first heat exchange surface second side 114/secondheat exchange surface first side 213). Non-limiting examples of secondheat exchange medium(s) can include those fluids comprising water,glycol, one or more hydrocarbons, or combinations thereof.

The processes and reaction systems described herein can use an organicreaction medium. Generally, the organic reaction can act as a solvent ora diluent in the processes described herein. In an aspect, the organicreaction medium can be a hydrocarbon, a halogenated hydrocarbon, or acombination thereof, for example. Hydrocarbons and halogenatedhydrocarbons which can be used as an organic reaction medium caninclude, for example, aliphatic hydrocarbons, aromatic hydrocarbons,petroleum distillates, halogenated aliphatic hydrocarbons, halogenatedaromatic hydrocarbons, or combinations thereof. Aliphatic hydrocarbonswhich can be useful as an organic reaction medium include C₃ to C₂₀aliphatic hydrocarbons, or C₄ to C₁₅ aliphatic hydrocarbons, or C₅ toC₁₀ aliphatic hydrocarbons, for example. The aliphatic hydrocarbonswhich can be used as an organic reaction medium can be cyclic or acyclicand/or can be linear or branched, unless otherwise specified.Non-limiting examples of suitable acyclic aliphatic hydrocarbon organicreaction mediums that can be utilized singly or in any combinationinclude propane, iso-butane, n-butane, butane (n-butane or a mixture oflinear and branched C₄ acyclic aliphatic hydrocarbons), pentane(n-pentane or a mixture of linear and branched C₅ acyclic aliphatichydrocarbons), hexane (n-hexane or mixture of linear and branched C₆acyclic aliphatic hydrocarbons), heptane (n-heptane or mixture of linearand branched C₇ acyclic aliphatic hydrocarbons), octane (n-octane or amixture of linear and branched C₈ acyclic aliphatic hydrocarbons), orcombinations thereof. Non-limiting examples of suitable cyclic aliphatichydrocarbons which can be used as an organic reaction medium includecyclohexane, and methyl cyclohexane, for example. Aromatic hydrocarbonswhich can be useful as an organic reaction medium include C₆ to C₁₀aromatic hydrocarbons. Non-limiting examples of suitable aromatichydrocarbons that can be utilized singly or in any combination as anorganic reaction medium include benzene, toluene, xylene (includingortho-xylene, meta-xylene, para-xylene, or mixtures thereof),ethylbenzene, or combinations thereof. Halogenated aliphatichydrocarbons which can be useful as an organic reaction medium includeC₁ to C₁₅ halogenated aliphatic hydrocarbons. C₁ to C₁₀ halogenatedaliphatic hydrocarbons, or C₁ to C₅ halogenated aliphatic hydrocarbons,for example. The halogenated aliphatic hydrocarbons which can be used asan organic reaction medium can be cyclic or acyclic and/or can be linearor branched, unless otherwise specified. Non-limiting examples ofsuitable halogenated aliphatic hydrocarbons which can be utilized as anorganic reaction medium include methylene chloride, chloroform, carbontetrachloride, dichloroethane, trichloroethane, and combinationsthereof. Halogenated aromatic hydrocarbons which can be useful as anorganic reaction medium include C₆ to C₂₀ halogenated aromatichydrocarbons, or C₆ to C₁₀ halogenated aromatic hydrocarbons, forexample. Non-limiting examples of suitable halogenated aromatichydrocarbons which can be used as a solvent include chlorobenzene,dichlorobenzene, or combinations thereof, for example.

The choice of organic reaction medium can be made on the basis ofconvenience in processing. For example, isobutane can be chosen to becompatible with solvents and diluents used in processes using theproduct(s) of the process described herein (e.g., using the product forthe formation of polymer in a subsequent processing step). In someembodiments, the organic reaction medium can be chosen to be easilyseparable from the one or more of the oligomers in the oligomer product.In some embodiments, an oligomer of the oligomer product can be utilizedas the reaction system solvent. For example, when 1-hexene is anoligomer of an ethylene trimerization process, 1-hexene can be chosen asthe reaction system solvent to decrease the need for separation.

Generally, the operating parameters for the reaction zone 101 aredisclosed in U.S. Patent Application Publication No. 2017/00812570081256to Kreischer, entitled “Design of an EthyleneOligomerization/Trimerization/Tetramerization Reactor”.

For any process, reaction system, or heat exchange system describedherein, the reaction zone (i.e., reaction zone 101) can operate at anypressure that can facilitate the desired oligomerization (e.g.,trimerization, tetramerization, or trimerization and tetramerization ofan olefin, for example, ethylene). In an aspect, the reaction zone(reaction zone 101) can operate at any pressure that produces thedesired oligomer product (e.g., a trimerization product, tetramerizationproduct, or trimerization and tetramerization product). In some aspects,the oligomer product can be formed at a pressure greater than or equalto 0 psig (0 KPa), 50 psig (344 KPa), 100 psig (689 KPa), or 150 psig(1.0 MPa). In other aspects, the oligomer product can be formed at apressure ranging from 0 psig (0 KPa) to 2,500 psig (17.3 MPa), 0 psig(KPa) to 1,600 psig (11.0 MPa), 0 psig (KPa) to 1,500 psig (10.4 MPa),50 psig (344 KPa) to 2,500 psig (17.3 MPa), 100 psig (689 KPa) to 2,500psig (17.3 MPa), 150 psig (1.0 MPa) to 2,000 psig (13.8 MPa), or 300psig (2.0 MPa) to 900 psig (6.2 MPa). In an aspect, the oligomer productcan be formed at an ethylene pressure (or ethylene partial pressure)greater than or equal to 0 psig (0 KPa), 50 psig (344 KPa), 100 psig(689 KPa), or 150 psig (1.0 MPa). In other aspects, the ethylenepressure (or ethylene partial pressure) at which the ethylene oligomerproduct can be formed can range from 0 psig (0 KPa) to 2,500 psig (17.3MPa), 50 psig (345 KPa) to 2,500 psig (17.3 MPa), 100 psig (689 KPa) to2,500 psig (17.3 MPa), or 150 psig (1.0 MPa) to 2,000 psig (13.8 MPa).In other aspects, the ethylene pressure (or ethylene partial pressure)at which the ethylene oligomer product can be formed can range from 500psig (3.45 MPa) to 5,000 psig (34.5 MPa), 1,000 psig (6.89 MPa) to 5,000psig (34.5 MPa), 2,000 psig (13.8 MPa) to 5,000 psig (34.5 MPa), 3,000psig (20.7 MPa) to 5,000 psig (34.5 MPa), 500 psig (3.44 MPa) to 4,000psig (27.6 MPa), 1,000 psig (6.89 MPa) to 4,000 psig (27.6 MPa), or 1000psig (6.89 MPa) to 3,500 psig (24.1 MPa).

For any process or reaction system described herein, the oligomerproduct can be formed (or the reaction zone can operate) at a minimumhydrogen partial pressure of 1 psi (6.9 kPa), 2 psi (14 kPa); 5 psi (34kPa), 10 psi (69 kPa), or 15 psi (103 kPa); alternatively oradditionally at a maximum hydrogen partial pressure of 200 psi (1.4MPa), 150 psi (1.03 MPa), 100 psi (689 kPa), 75 psig (517 kPa), or 50psi (345 kPa). In an embodiment, the oligomer product can be formed (orthe reaction zone can operate) at a hydrogen partial pressure rangingfrom any minimum hydrogen partial pressure disclosed herein to anymaximum hydrogen partial pressure disclosed herein. In some non-limitingembodiments wherein hydrogen is utilized, the oligomer product can beformed (or the reaction zone can operate) at a hydrogen partial pressurefrom 1 psi (6.9 kPa) to 200 psi (1.4 MPa), from 5 psi (34 kPa) to 150psi (1.03 MPa), from 10 psi (69 kPa) to 100 psi (689 kPa), or from 15psi (100 kPa) to 75 psig (517 kPa). Other hydrogen partial pressureranges that can be utilized are readily apparent to those skilled in theart with the aid of this disclosure.

In other aspects wherein hydrogen is utilized, the oligomer product canbe formed (or the reaction zone can operate) at a minimum hydrogen toethylene mass ratio of (0.05 g hydrogen)/(kg ethylene), (0.1 ghydrogen)/(kg ethylene), (0.25 g hydrogen)/(kg ethylene), (0.4 ghydrogen)/(kg ethylene), or (0.5 g hydrogen)/(kg ethylene);alternatively or additionally, at a maximum hydrogen to ethylene massratio can be (5 g hydrogen)/(kg ethylene), (3 g hydrogen)/(kg ethylene),(2.5 g hydrogen)/(kg ethylene), (2 g hydrogen)/(kg ethylene), or (1.5 ghydrogen)/(kg ethylene). In an embodiment, the oligomer product can beformed (or the reaction zone can operate) at a hydrogen to ethylene massratio ranging from any minimum hydrogen to ethylene mass ratio disclosedherein to any maximum hydrogen to ethylene mass ratio disclosed herein.In some non-limiting embodiments, the oligomer product can be formed (orthe reaction zone can operate) at a hydrogen to ethylene mass ratio from(0.05 g hydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from(0.25 g hydrogen)/(kg ethylene) to (5 g hydrogen)/(kg ethylene), from(0.25 g hydrogen)/(kg ethylene) to (4 g hydrogen)/(kg ethylene), from(0.4 g hydrogen)/(kg ethylene) to (3 g hydrogen)/(kg ethylene), from(0.4 g hydrogen)/(kg ethylene) to (2.5 g hydrogen)/(kg ethylene), from(0.4 g hydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene), or from(0.5 g hydrogen)/(kg ethylene) to (2 g hydrogen)/(kg ethylene). Otherhydrogen to ethylene mass ratio ranges that can be utilized are readilyapparent to those skilled in the art with the aid of this disclosure.

For any process, reaction system, or heat exchange system describedherein, the temperature (or average temperature) at which the oligomerproduct (e.g., trimerization product, tetramerization product, ortrimerization and tetramerization product) can be formed in the reactionzone (i.e., reaction zone 101) can be a minimum temperature of 0° C.,25° C., 40° C., 50° C. 60° C. 70° C., or 75° C.; alternatively oradditionally, a maximum temperature of 120° C., 110° C., 100° C., or 95°C., or 90° C. the temperature (or average temperature) at which theoligomer product (e.g., trimerization product, tetramerization product,or trimerization and tetramerization product) can be formed in thereaction zone (i.e., reaction zone 101) can range from any minimumtemperature (or average temperature) disclosed herein to any maximumtemperature (or average temperature) disclosed herein. Non-limitingtemperature (or average temperatures) at which the oligomer product(e.g., trimerization product, tetramerization product, or trimerizationand tetramerization product) can be formed can range from 0° C. to 120°C., from 25° C. to 120° C., from 40° C. to 110° C., from 50° C. to 100°C., from 50° C. to 100° C., from 60° C. to 95° C., from 70° C. to 95°C., from 75° C. to 95° C., or from 75° C. to 90° C.). Other suitableranges for the temperature (or average temperatures) at which theoligomer product (e.g., trimerization product, tetramerization product,or trimerization and tetramerization product) can be formed are readilyapparent from the present disclosure.

For any process or reaction system described herein, the reaction time(or average reaction time) that the reaction mixture spends in thereaction zone (i.e., reaction zone 101) can comprise any time that canproduce the desired quantity of oligomer product; alternatively, anytime that can provide a desired catalyst system productivity;alternatively, any time that can provide a desired conversion of olefin(e.g., ethylene). For example, the olefin monomer (e.g., ethylenemonomer) conversion can be at least 30 wt. %; alternatively, at least 35wt. %; alternatively, at least 40 wt. %; alternatively, at least 45 wt.%.

For any process or reaction system described herein, the oligomerproduct is an ethylene trimerization product that comprises at least 70wt. % hexene; alternatively, at least 75 wt. % hexene; alternatively, atleast 80 wt. % hexene; alternatively, at least 85 wt. % hexene; oralternatively, at least 90 wt. % hexene based upon the weight of theoligomer product. In some aspects, the ethylene trimerization productcan comprise from 70 wt. % to 99.8 wt. % hexene; alternatively, from 75wt. % to 99.7 wt. % hexene; or alternatively, from 80 wt. % to 99.6 wt.% hexene based upon the weight of the ethylene trimerization product.

For any process or reaction system described herein, the oligomerproduct is an ethylene tetramerization product that comprises at least70 wt. % octene; alternatively, at least 75 wt. % octene; alternatively,at least 80 wt. % octene; alternatively, at least 85 wt. % octene; oralternatively, at least 90 wt. % octene based upon the weight of theethylene tetramerization product. In some aspects, the ethylenetetramerization product can comprise from 70 wt. % to 99.8 wt. % octene;alternatively, from 75 wt. % to 99.7 wt. % octene; or alternatively,from 80 wt. % to 99.6 wt. % octene based upon the weight of the ethylenetetramerization product.

For any process or reaction system described herein, the oligomerproduct is an ethylene trimerization and tetramerization product thatcomprises at least 70 wt. % hexene and octene; alternatively, at least75 wt. % hexene and octene; alternatively, at least 80 wt. % hexene andoctene; alternatively, at least 85 wt. % hexene and octene; oralternatively, at least 90 wt. % hexene and octene based upon the weightof the ethylene trimerization and tetramerization product. In otheraspects, the ethylene trimerization and tetramerization product cancomprise from 70 wt. % to 99.8 wt. % hexene and octene; alternatively,from 75 wt. % to 99.7 wt. % hexene and octene; or alternatively, from 80wt. % to 99.6 wt. % hexene and octene based upon the weight of theethylene trimerization and tetramerization product.

For any process or reaction system described herein, where the oligomerproduct is an ethylene trimerization product or an ethylenetrimerization and tetramerization product, the ethylene trimer cancomprise at least 85 wt. % 1-hexene; alternatively, at least 87.5 wt. %1-hexene; alternatively, at least 90 wt. % 1-hexene; alternatively, atleast 92.5 wt. % 1-hexene; alternatively, at least 95 wt. % 1-hexene;alternatively, at least 97 wt. % 1-hexene; or alternatively, at least 98wt. % 1-hexene by weight of the ethylene trimer, or from 85 wt. % to99.9 wt. % 1-hexene; alternatively, from 87.5 wt. % to 99.9 wt. %1-hexene; alternatively, from 90 wt. % to 99.9 wt. % 1-hexene;alternatively, from 92.5 wt. % to 99.9 wt. % 1-hexene; alternatively,from 95 wt. % to 99.9 wt. % 1-hexene; alternatively, from 97 wt. % to99.9 wt. % 1-hexene; or alternatively, from 98 wt. % to 99.9 wt. %1-hexene by weight of the ethylene trimer.

For any process or reaction system described herein, where the oligomerproduct is an ethylene tetramerization or ethylene trimerization andtetramerization product, the ethylene tetramer can comprise at least 85wt. % 1-octene; alternatively, at least 87.5 wt. % 1-octene;alternatively, at least 90 wt. % 1-octene; alternatively, at least 92.5wt. % 1-octene; alternatively, at least 95 wt. % 1-octene;alternatively, at least 97 wt. % 1-octene; or alternatively at least 98wt. % I-octene by weight of the ethylene tetramer or from 85 wt. % to99.9 wt. % 1-octene; alternatively, from 87.5 wt. % to 99.9 wt. %1-octene; alternatively, from 90 wt. % to 99.9 wt. % 1-octene;alternatively, from 92.5 wt. % to 99.9 wt. % 1-octene; alternatively,from 95 wt. % to 99.9 wt. % 1-octene; alternatively, from 97 wt. % to99.9 wt. % 1-octene; or alternatively, from 98 wt. % to 99.9 wt. %1-octene by weight of the ethylene tetramer.

Additional Disclosure

The following is provided as additional disclosure for combinations offeatures and aspects of the present invention.

Statement 1. A process comprising: controlling (or providing) a reactionmixture temperature within the reaction zone with a heat exchangesystem, the heat exchange system comprising a first heat exchangerproviding indirect contact between at least a portion of the reactionmixture and a first heat exchange medium, the first heat exchangercomprising a first heat exchange surface having i) a first heat exchangesurface first side in contact with at least a portion of the reactionmixture, and ii) a first heat exchange surface second side in contactwith the first heat exchange medium; where a pressure on the first heatexchange surface second side can be (or can be controlled to be) anypressure less than 1 atmosphere (101.3 kPa) described herein (e.g., lessthan 1 atmosphere; a minimum pressure of 0.1, 0.12, 0.15, 0.2, 0.25,0.3, 0.375, or 0.45 atmospheres; a maximum pressure, 0.9, 0.875, 0.85,0.8, 0.75, or 0.7 atmospheres; or range from 0.1 to 0.9, 0.12 to 0.9,0.15 to 0.875, 0.2 to 0.875, 0.3 to 0.85, 0.375 to 0.85, or 0.45 to 0.85atmospheres; among other pressures disclosed herein).

Statement 2. The process of Statement 1 fiurther comprising providing(or controlling) the pressure on the first heat exchange surface secondside to provide (or control) the reaction mixture temperature within thereaction zone.

Statement 3. A process comprising: providing (or controlling) a pressurein a heat exchange system to provide (or control) a reaction mixturetemperature within a reaction zone, the heat exchange system comprisinga first heat exchanger providing indirect contact between the reactionmixture and a first heat exchange medium, the first heat exchangercomprising a first heat exchange surface having i) a first heat exchangesurface first side in contact with the reaction mixture, and ii) a firstheat exchange surface second side in contact with the first heatexchange medium; where a pressure on the first heat exchange surfacesecond side of the first heat exchanger can be (or can be controlled tobe) any pressure less than 1 atmosphere (101.3 kPa) described herein(e.g., less than 1 atmosphere; a minimum pressure of 0.1, 0.12, 0.15,0.2, 0.25, 0.3, 0.375, or 0.45 atmospheres; a maximum pressure, 0.9,0.875, 0.85, 0.8, 0.75, or 0.7 atmospheres; or range from 0.1 to 0.9,0.12 to 0.9, 0.15 to 0.875, 0.2 to 0.875, 0.3 to 0.85, 0.375 to 0.85, or0.45 to 0.85 atmospheres; among other pressures disclosed herein).

Statement 4. The process of any one of Statements 1-3, where the firstheat exchange medium has a boiling point at 1 atmosphere (101.3 kPa)greater than an average reaction mixture temperature on the first heatexchange surface first side and a boiling point at the pressure on thefirst heat exchange surface second side less than the average reactionmixture temperature on the first heat exchange surface first side.

Statement 5. The process of any one of Statements 1-4, wherein a firstpart of the at least a portion of the reaction mixture on the first heatexchange surface first side indirectly contacts a liquid phase of thefirst heat exchange medium on the first heat exchange surface secondside and a second part of the at least a portion of the reaction mixtureon the first heat exchange surface first side indirectly contacts avapor phase of the first heat exchange medium on the first heat exchangesurface second side (providing a first level of liquid phase of thefirst heat exchange medium on the first heat exchange surface secondside).

Statement 6. The process of Statement 5, wherein a percentage of the atleast a portion of the reaction mixture on the first heat exchangesurface first side which indirectly contacts a liquid phase of the firstheat exchange medium on the first heat exchange surface second side canbe (or can be controlled to be) any percentage disclosed herein (e.g.,greater than or equal to 50%, 60%, 70%, 75%, 80%, or 90% by volume; lessthan or equal to 95%, 90%, 85%, 80%, 75%, or 70% by volume; or from 50%to 95%, from 60% to 95%, from 60% to 90%, from 70% to 90%, from 70% to85%, or from 75% to 85%, by volume; among other percentages disclosedherein).

Statement 7. The process of Statement 5 or 6, wherein a percentage ofthe surface area of the first heat exchange surface second side whichcontacts the liquid phase of the first heat exchange medium can be, orcan be controlled to be, any percentage disclosed herein (e.g., at least50%, 60%, 70%, 75%, 80%, or 90%; less than or equal to 95%, 90%, 85%,80%, 75%, or 70%; or range from 50% to 95%, from 60% to 95%, from 60% to90%, from 70% to 90%, from 70% to 85%, or from 75% to 85%; among otherpercentages disclosed herein).

Statement 8. The process of any one of Statements 5-7, wherein a volumeratio of the liquid phase of the first heat exchange medium in the firstheat exchanger (or on the first heat exchange surface second side) tothe vapor phase of the first heat exchange medium in the first heatexchanger (or on the first heat exchange surface second side) can be (orcan be controlled to be) any volume ratio disclosed herein (e.g.,greater than or equal to 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1;less than or equal to 20:1, 10:1, 6:1, 4:1, 3:1, or 2.5:1; or from 1:1to 20:1, from 1.5:1 to 20:1, from 1.5:1 to 9:1, from 2:1 to 9:1, from2.5:1 to 6:1, or from 3:1 to 6.1; among other ratios disclosed herein),wherein the heat exchange system further comprises one or more pressurecontrol devices.

Statement 9. The process of Statements 5-8, comprising controlling afirst level of a liquid phase of the first heat exchange medium on thefirst heat exchange surface second side.

Statement 10. The process of Statements 5-8, wherein controlling thereaction mixture temperature (or average reaction mixture temperature)comprises controlling a first level of a liquid phase of the first heatexchange medium on the first heat exchange surface second side

Statement 11. The process of Statement 10 or 11, wherein controlling thefirst level of the liquid phase of the first heat exchange mediumcomprises increasing or decreasing the flow rate of the first heatexchange medium.

Statement 12. The process of any one of Statements 1-11, where the heatexchange system further comprises one or more pressure control devicesproviding (or controlling) the pressure of less than 1 atmosphere (101.3kPa) on the first heat exchange surface second side.

Statement 13. The process of Statement 12, wherein the pressure on thefirst heat exchange surface first side (or the first heat exchangemedium) can be controlled (or provided) by a pressure set point of theone or more pressure control devices.

Statement 14. The process of Statement 13, wherein controlling thereaction mixture temperature (or average reaction mixture temperature)in the reaction zone comprises controlling the pressure set point of theone or more pressure control points.

Statement 15. The process of any one of Statements 1-4, wherein the heatexchange system further comprises a second heat exchanger providingindirect contact between the first heat exchange medium and a secondheat exchange medium, the second heat exchanger comprising a second heatexchange surface having i) a second heat exchange surface first side incontact with the first heat exchange medium, and ii) a second heatexchange surface second side in contact with the second heat exchangemedium; and where a pressure on the second heat exchange surface firstside of the second heat exchanger can be (or can be controlled to be)any pressure less than 1 atmosphere (101.3 kPa) described herein (e.g.,less than 1 atmosphere; a minimum pressure of 0.1, 0.12, 0.15, 0.2,0.25, 0.3, 0.375, or 0.45 atmospheres; a maximum pressure, 0.9, 0.875,0.85, 0.8, 0.75, or 0.7 atmospheres; or range from 0.1 to 0.9, 0.12 to0.9, 0.15 to 0.875, 0.2 to 0.875, 0.3 to 0.85, 0.375 to 0.85, or 0.45 to0.85 atmospheres).

Statement 16. The process of Statement 15, where the second heatexchange surface does not contact the reaction mixture.

Statement 17. The process of Statement 15 or 16, wherein the heatexchange system further comprises one or more pressure control devicesin fluid communication with the first heat exchange surface second sideand second heat exchange surface first side.

Statement 18. The process of Statement 17, where the heat exchangesystem further comprises a plurality of conduits connecting the firstheat exchanger and the second heat exchanger and allowing for flow ofthe first heat exchange medium between the first heat exchange surfacesecond side and the second heat exchange surface first side.

Statement 19. The process of Statement 18 where at least one of one ormore conduits allows for flow of the first heat exchange medium from thefirst heat exchange surface second side to the second heat exchangesurface first side and at least one of the one or more conduits allowsfor flow of the first heat exchange medium from the second heat exchangesurface first side to the first heat exchange surface second side.

Statement 20. The process of Statement 17 or 18, wherein at least one ofthe one or more pressure control devices is in [direct] fluidcommunication with at least one the one of the plurality of conduits.

Statement 21. The process of any one of Statements 17-20, wherein theone or more pressure control devices provides (or controls) the pressureof less than 1 atmosphere (101.3 kPa) on the first heat exchange surfacesecond side and on the second heat exchange surface first side and/orcontrols the pressure of less than 1 atmosphere (101.3 kPa) on the firstheat exchange surface second side and on the second heat exchangesurface first side.

Statement 22. The process of Statement 21, wherein the pressure on thefirst heat exchange surface first side and on the second heat exchangesurface first side can be controlled by a pressure set point on one ofthe one or more pressure control devices.

Statement 23. The process of any one of Statements 19-22, whereincontrolling the reaction mixture temperature (or average reactionmixture temperature) comprises controlling the pressure on the firstheat exchange surface first side and on the second heat exchange surfacefirst side by controlling the pressure provided by the one or morepressure control devices.

Statement 24. The process of any one of Statements 15-23, wherein afirst part of the at least a portion of the reaction mixture on thefirst heat exchange surface first side indirectly contacts a liquidphase of the first heat exchange medium on the first heat exchangesurface second side and a second part of the at least a portion of thereaction mixture on the first heat exchange surface first sideindirectly contacts a vapor phase of the first heat exchange medium onthe first heat exchange surface second side (providing a first level ofliquid phase of the first heat exchange medium on the first heatexchange surface second side), and wherein at least a first part of thesecond heat exchange medium on the second heat exchange surface secondside indirectly contacts the vapor phase of the first heat exchangemedium on the second heat exchange surface first side and a second partof the second heat exchange medium on the second heat exchange surfacesecond side indirectly contacts liquid phase of the first heat exchangemedium on the second heat exchange surface first side (providing asecond level of liquid phase of the first heat exchange medium on thesecond heat exchange surface first side).

Statement 25. The process of Statement 24, wherein a percentage of theat least a portion of the reaction mixture on the first heat exchangesurface first side which indirectly contacts a liquid phase of the firstheat exchange medium on the first heat exchange surface second side canbe (or can be controlled to be) any percentage disclosed herein (e.g.,greater than or equal to 50%, 60%, 70%, 75%, 80%, or 90% by volume; lessthan or equal to 95%, 90%, 85%, 80%, 75%, or 70% by volume; or from 50%to 95%, from 60% to 95%, from 60% to 90%, from 70% to 90%, from 70% to85%, or from 75% to 85%, by volume; among other percentages disclosedherein).

Statement 26. The process of Statement 24 or 25, wherein a percentage ofthe surface area of the first heat exchange surface second side whichcontacts the liquid phase of the first heat exchange medium can be, orcan be controlled to be, any percentage disclosed herein (e.g., at least50%, 60%, 70%, 75%, 80%, or 90%; less than or equal to 95%, 90%, 85%,80%, 75%, or 70%; or range from 50% to 95%, from 60% to 95%, from 60% to90%, from 70% to 90%, from 70% to 85%, or from 75% to 85%; among otherpercentages disclosed herein).

Statement 27. The process of any one of Statements 24-26, wherein avolume ratio of the liquid phase of the first heat exchange medium inthe first heat exchanger (or on the first heat exchange surface secondside) to the vapor phase of the first heat exchange medium in the firstheat exchanger (or on the first heat exchange surface second side) canbe (or can be controlled to be) any volume ratio disclosed herein (e.g.,greater than or equal to 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1;less than or equal to 20:1, 10:1, 6:1, 4:1, 3:1, or 2.5:1; or from 1:1to 20:1, from 1.5:1 to 20:1, from 1.5:1 to 9:1, from 2:1 to 9:1, from2.5:1 to 6:1, or from 3:1 to 6.1; among other ratios disclosed herein),wherein the heat exchange system further comprises one or more pressurecontrol devices

Statement 28. The process of any one of Statement 24-27, wherein apercentage of the second heat exchange medium on the second heatexchange surface second side which indirectly contacts the liquid phaseof the first heat exchange medium on the second heat exchange surfacefirst side can be (or can be controlled to be) any percentage disclosedherein (e.g., greater than or equal to 50%, 60%, 70%, 80%, or 90%, byvolume; less than or equal to 95%, 90%, 85%, 80%, 75%, or 70%, byvolume; or from 50% to 95%, from 60% to 95%, from 60% to 90%, from 70%to 90%, from 70% to 85%, or from 75% to 85%, by volume

Statement 29. The process of any one of Statements 24-28, wherein avolume ratio of the liquid phase of the first heat exchange medium inthe second heat exchanger (or on the second heat exchange surface firstside) to the vapor phase of the first heat exchange medium in the secondheat exchanger (or on the second heat exchange surface first side) canbe (or can be controlled to be) any volume ratio disclosed herein (e.g.,greater than or equal to 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, or 4:1;less than or equal to 20:1, 10:1, 6:1, 4:1, 3:1, or 2.5:1; or from 1:1to 20:1, from 1.5:1 to 20:1, from 1.5:1 to 9:1, from 2:1 to 9:1, from2.5:1 to 6:1, or from 3:1 to 6.1).

Statement 30. The process of Statement 24-29, wherein controlling thereaction mixture temperature (or average reaction mixture temperature)comprises controlling the pressure on the first heat exchange surfacesecond side, controlling the first level of the liquid phase of thefirst heat exchange medium on the first heat exchange surface secondside, controlling the second level of the liquid phase of the first heatexchange medium on the second heat exchange surface first side, or anycombination thereof.

Statement 31. The process of any one of Statements 24-29, whereincontrolling the reaction mixture temperature comprises controlling thefirst level of the liquid phase of the first heat exchange medium on thefirst heat exchange surface second side.

Statement 32. The process of Statement 31, wherein the first level ofthe liquid phase of the first heat exchange medium on the first heatexchange surface second side comprises a) controlling a second level ofa liquid phase of the first heat exchange medium on the second heatexchange surface first side b) adding first heat exchange medium to theheat exchange system or removing a portion of the first heat exchangemedium from the heat exchange system, c) controlling the pressure on thefirst heat exchange surface second side (and/or first heat exchangemedium, and/or second heat exchange surface first side, or d) anycombination thereof.

Statement 33. The process of any one of Statements 15-32, wherein asecond level of the liquid phase of the first heat exchange medium onthe second heat exchange surface first side is vertically higherrelative to a common reference point on the ground than the first levelof the liquid phase of the first heat medium on the first heat exchangesurface second side.

Statement 34. The process of any one of Statements 15-33, wherein thesecond heat exchange surface comprises vertically oriented tubes orplates.

Statement 35. The process of any one of Statements 1-34, wherein thefirst heat exchange surface comprises horizontally oriented tubes orplates.

Statement 36. The process ofany one of Statements 1-35, wherein thereaction mixture temperature (or average reaction mixture temperature)in the reaction zone (or on the first heat exchange surface first side)can have any values disclosed herein (e.g., a minimum temperature of 0°C. 25° C. 40° C. 50° C. 60° C., 70° C. or 75° C.; a maximum temperatureof 120° C., 110° C., 100° C. or 95° C., or 90° C.; in a range from 0° C.to 120° C., from 25° C. to 120° C., from 40° C. to 110° C. from 50° C.to 100° C., from 50° C. to 100° C., from 60° C. to 95° C., from 70° C.to 95° C., from 75° C. to 95° C., or from 75° C. to 90° C.).

Statement 37. The process of any one of Statements 1-36, wherein thefirst heat exchange medium has any boiling point at 1 atmosphere (101.3kPa) disclosed herein (e.g., a minimum of 40, 50, 60, or 70° C.; amaximum of 150, 140, 130, 120, or 110° C.; or in a range from 40 to 150°C., 50 to 140° C., 60 to 130° C., 70 to 120° C., or 70 to 110° C., amongothers disclosed herein).

Statement 38. The process ofany one of Statement 1-37, wherein in thefirst heat exchange medium comprises any organic heat exchange medium orinorganic heat exchange medium disclosed herein.

Statement 39. The process of any one of Statements 1-38, wherein thefirst heat exchange medium comprises water.

Statement 40. The process of any one of Statements 1-30, wherein a ratioof heat exchanged reaction mixture volume to the total reaction mixturevolume within the reaction zone can have value disclosed herein (e.g., aminimum value of 1:1, 1.5:1, 2:1, 2.5:1, 3:1, or 4:1; a maximum value of100:1, 50:1, 20:1, 15:1, 12:1, or 9:1; or in a range from 1:1 to 100:1,from 1.5:1 to 100:1, from 2:1 to 100:1, from 3:1 to 100:1, from 4:1 to100:1, from 3:1 to 50:1, from 3:1 to 20:1, from 4:1 to 50:1, from 4:1 to15:1, or from 4:1 to 12:1; among others disclosed herein).

Statement 41. The process of any one of Statements 1-40, where atemperature difference between an average reaction mixture temperatureon the first heat exchange surface first side and a first heat exchangemedium temperature on the first heat exchange surface second side can be(or can be controlled to be) any temperature difference disclosed herein(e.g., less than 20° C., 15° C., 10° C., 7.5° C., 5° C., 4° C., or 3°C.).

Statement 42. The process of any one of Statements 1-41, wherein thefirst heat exchange medium temperature on the first heat exchangesurface second side can be (or can be controlled to be) within anypercentage of an average reaction mixture temperature on the first heatexchange surface first side disclosed herein (e.g., 20%, 15%, 12.5%,10%, 7.5%, 6%, 5%, or 4.5%).

Statement 43. The process of any one of Statements 1-42, wherein areaction mixture temperature at any point in the reaction zone can be,or can be controlled to be, within any value of an average reactionmixture temperature in the reaction zone disclosed herein (e.g., within15° C., 10° C., 7.5° C., 5° C., 4° C., 3° C., or 2° C.).

Statement 44. The process of any one of Statements 1-43, wherein areaction mixture temperature at any point in the reaction zone can be,or can be controlled to be, within any percentage of an average reactionmixture temperature in the reaction zone disclosed herein (e.g., within3%, 2%, 1.5%, 1%, 0.8%, 0.6%, 0.5%, 0.45%, 0.4%, 0.35%, 0.3%, 0.25%, or0.2%).

Statement 45. The process of any one of Statements 1-44, wherein theprocess is selected from the group consisting of an ethyleneoligomerization process, an ethylene trimerization process, an ethylenetetramerization process, or an ethylene trimerization andtetramerization process.

Statement 46. The process of any one of Statements 1-45, comprisingintroducing at least 1) ethylene, 2) a catalyst system comprising i) aheteroatomic ligand transition metal compound complex and anyorganoaluminum compound, or ii) any heteroatomic ligand, a transitionmetal compound, and an organoaluminum compound, 3) optionally, a firstorganic reaction medium, and 4) optionally, hydrogen into a reactionmixture within a reaction zone; and forming an oligomer product in thereaction zone.

Statement 101. A reaction system comprising: a) a reaction zonecontaining a reaction mixture; and b) a heat exchange system comprisinga first heat exchanger configured to provide indirect contact between atleast a portion of the reaction mixture and a first heat exchangemedium, the first heat exchanger comprising a first heat exchangesurface having i) a first heat exchange surface first side configured tocontact the reaction mixture, and ii) a first heat exchange surfacesecond side configured to contact a first heat exchange medium; where apressure on the first heat exchange surface second side of the firstheat exchanger is any pressure less than 1 atmosphere (101.3 kPa)described herein (e.g., less than 1 atmosphere; a minimum pressure of0.1, 0.12, 0.15, 0.2, 0.25, 0.3, 0.375, or 0.45 atmospheres; a maximumpressure, 0.9, 0.875, 0.85, 0.8, 0.75, or 0.7 atmospheres; or range from0.1 to 0.9, 0.12 to 0.9, 0.15 to 0.875, 0.2 to 0.875, 0.3 to 0.85, 0.375to 0.85, or 0.45 to 0.85 atmospheres).

Statement 102. The reaction system Statement 101, wherein the heatexchange system further comprises one or more pressure control devicesin fluid communication with the first heat exchange surface second sideand configured to measure, provide and/or control the pressure of lessthan 1 atmosphere (101.3 kPa) on the first heat exchange surface secondside.

Statement 103. The reaction system of Statement 101 or 102, wherein afirst part of the at least a portion of the reaction mixture on thefirst heat exchange surface first side (or a first part of a surfacearea of the first heat exchange surface second side) indirectly contactsa liquid phase of the first heat exchange medium on the first heatexchange surface second side and a second part of the at least a portionof the reaction mixture on the first heat exchange surface first side(or a second part of the surface area of the first heat exchange surfacesecond side) indirectly contacts a vapor phase of the first heatexchange medium on the first heat exchange surface second side(providing a first level of liquid phase of the first heat exchangemedium on the first heat exchange surface second side).

Statement 104. The reaction system of any one of Statements 101-103,wherein the heat exchange system further comprises a first levelindicator and/or controller (coupled to the first heat exchanger and)configured to measure, monitor, and/or control a first level of theliquid phase of the first heat exchange medium on the first heatexchange surface second side.

Statement 105. The reaction system of Statement 104, wherein the firstlevel indicator and/or controller (coupled to the first heat exchangerand) is configured to control the first level of liquid phase of thefirst heat exchange medium of the first heat exchange surface first sideto be a) any percentage of the at least a portion of the reactionmixture on the first heat exchange surface first side which indirectlycontacts a liquid phase of the first heat exchange medium on the firstheat exchange surface second side disclosed herein, b) any percentage ofthe surface area of the first heat exchange surface second side whichcontacts the liquid phase of the first heat exchange medium disclosedherein, c) any volume ratio of the liquid phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) to the vapor phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) disclosed herein, or d) any combinationthereof.

Statement 106. The reaction system of Statement 104 or 105, wherein theheat exchange system further comprises a first heat exchange medium flowcontrol valve configured to control the flow rate of the first heatexchange medium.

Statement 107. The reaction system of Statement 106, wherein the firstlevel indicator and/or controller is configured to actuate the heatexchange medium flow control valve to control the level of liquid phaseof the of first heat exchange medium on the first heat exchange surfacesecond side.

Statement 108. The reaction system of Statements 101-107, wherein thereaction system further comprises a temperature indicator and/orcontroller configured to measure and/or control the reaction mixturetemperature (or average reaction mixture temperature) within thereaction zone.

Statement 109. The reaction system of Statement 109, wherein thetemperature indicator and/or controller is a) coupled to at least one ofthe pressure control devices of Statements 101 or 102 and configured toactuate a control mechanism to control a pressure set point of the oneor more pressure control devices in response to reaction mixturetemperature (or average reaction mixture temperature), b) is coupledwith the first level indicator or controller of statement 104 or 105, c)the first heat exchange medium flow control valve of statements 106 or107 and configured to actuate a heat exchange medium flow control valveto control the flow rate of first level of liquid phase of the firstheat exchange medium on the first heat exchange surface second side inresponse to the reaction mixture temperature (or average reactionmixture temperature), or d) a combination thereof.

Statement 110. The reaction system of any one of Statement 101, whereinthe heat exchange system further comprises a second heat exchangerconfigured to provide indirect contact between the first heat exchangemedium and a second heat exchange medium, the second heat exchangercomprising a second heat exchange surface having i) a second heatexchange surface first side configured to contact the first heatexchange medium and ii) a second heat exchange surface second sideconfigured to contact the second heat exchange medium; where a pressureon the second heat exchange surface first of the second heat exchangeris any pressure less than 1 atmosphere (101.3 kPa) described herein(e.g., less than 1 atmosphere; a minimum pressure of 0.1, 0.12, 0.15,0.2, 0.25, 0.3, 0.375, or 0.45 atmospheres; a maximum pressure, 0.9,0.875, 0.85, 0.8, 0.75, or 0.7 atmospheres; or range from 0.1 to 0.9,0.12 to 0.9, 0.15 to 0.875, 0.2 to 0.875, 0.3 to 0.85, 0.375 to 0.85, or0.45 to 0.85 atmospheres).

Statement 111. The reaction system of Statement 108, wherein the secondheat exchange surface does not contact the reaction mixture.

Statement 112. The reaction system of Statement 110 or 111, wherein theheat exchange system further comprises a plurality of conduitsconfigured to fluidly connect the first heat exchanger and the secondheat exchanger and configured to allow for flow of the first heatexchange medium between the first heat exchange surface second side andthe second heat exchange surface first side.

Statement 113. The reaction system of Statement 112, wherein at leastone of one or more conduits allows for flow of the first heat exchangemedium from the first heat exchange surface second side to the secondheat exchange surface first side and at least one of the one or moreconduits allows for flow of the first heat exchange medium from thesecond heat exchange surface first side to the first heat exchangesurface second side.

Statement 114. The reaction system of any one of Statements 110-113,wherein a first part of the at least a portion of the reaction mixtureon the first heat exchange surface first side indirectly (or a firstpart of the surface area of the first heat exchange surface second side)contacts a liquid phase of the first heat exchange medium on the firstheat exchange surface second side and a second part of the at least aportion of the reaction mixture on the first heat exchange surface firstside indirectly (or a second part of the surface area of the first heatexchange surface second side) contacts a vapor phase of the first heatexchange medium on the first heat exchange surface second side(providing a first level of liquid phase of the first heat exchangemedium on the first heat exchange surface second side), and wherein atleast a first part of the second heat exchange medium on the second heatexchange surface second side indirectly (or a first part of the surfacearea of the second heat exchange surface first side) contacts the vaporphase of the first heat exchange medium on the second heat exchangesurface first side and a second part of the second heat exchange mediumon the second heat exchange surface second side indirectly contactsliquid phase of the first heat exchange medium on the second heatexchange surface first side (providing a second level of liquid phase ofthe first heat exchange medium on the second heat exchange surface firstside).

Statement 115. The reaction system of Statement 114, wherein at leastone of the plurality of conduits allows for flow of the vapor phase ofthe first heat exchange medium from the first heat exchange surfacesecond side to the second heat exchange surface first side and at leastone of the plurality of conduits allows for flow of the liquid phase offirst heat exchanger medium from the second heat exchange surface firstside to the first heat exchange surface second side.

Statement 116. The reaction system of any one of Statements 112-115,wherein the first heat exchanger, the second heat exchanger and theplurality of conduits are configured to fluidly connect the first heatexchanger and the second heat exchanger form a first heat exchangemedium circulation loop.

Statement 117. The reaction system of any one of Statements 110-116,where the heat exchange system further comprises one or more pressurecontrollers in fluid communication with the first heat exchange surfacesecond side and the second heat exchange surface first side, the one ormore pressure controllers configured to measure, provide, and/or controlany pressure disclosed herein on the first heat exchange surface secondside and the second heat exchange surface first side.

Statement 118. The reaction system of any one of Statements 112-116,where the heat exchange system further comprises one or more pressurecontrollers in direct fluid communication at least one of the pluralityof conduits, the one or more pressure controllers configured to measure,provide, and/or control any pressure disclosed herein on the first heatexchange surface second side and the second heat exchange surface firstside.

Statement 119. The reaction system of any one of Statements 113-116,where the heat exchange system further comprises one or more pressurecontrollers in direct fluid communication at least one of the pluralityof conduits allowing for flow of the first heat exchange medium from thefirst heat exchange surface second side to the second heat exchangesurface first side, the one or more pressure controllers configured tomeasure, provide, and/or control any pressure disclosed herein on thefirst heat exchange surface second side and the second heat exchangesurface first side.

Statement 120. The reaction system of any one of Statements 114-116,where the heat exchange system further comprises one or more pressurecontrollers in direct fluid communication with the at least one of theplurality of conduits allowing for flow of the vapor phase of the firstheat exchange medium from the first heat exchange surface second side tothe second heat exchange surface first side, the one or more pressurecontrollers configured to measure, provide, and/or control any pressuredisclosed herein on the first heat exchange surface second side and thesecond heat exchange surface first side.

Statement 121. The reaction system of any one of Statements 102 or117-120, wherein the one or more pressure control devices includes aneductor.

Statement 122. The reaction system of any one of Statements 102 or117-121, wherein the one or more pressure control devices includes acontrol valve.

Statement 123. The reaction system of Statement 122, wherein the eductorhas a motive fluid inlet fluidly connected to the control valve and asuction inlet fluidly connected to the first heat exchange surfacesecond side.

Statement 124. The reaction system of Statement 123, wherein one of theat least one pressure controllers actuate the control valve to provide amotive fluid to the motive fluid inlet of the eductor to provide thepressure of less than 1 atmosphere (101.3 kPa) on the first heatexchange surface second side.

Statement 125. The reaction system of Statement 122 or 123, wherein thepressure controller is configured to actuate the control valve betweenan open position and a closed position such that non-condensablecomponents in the first heat exchange medium are removed from the firstheat exchange medium.

Statement 126. The reaction system of any one of Statements 110-123,wherein the heat exchange system further comprises a first levelindicator and/or controller (coupled to the first heat exchanger and)configured to measure, monitor, and/or control the first level of theliquid phase of the first heat exchange medium on the first heatexchange surface second side.

Statement 127. The reaction system of Statement 125, wherein the firstlevel indicator and/or controller (coupled to the first heat exchangerand) is configured to control the first level of liquid phase of thefirst heat exchange medium on the first heat exchange surface secondside to be a) any percentage of the at least a portion of the reactionmixture on the first heat exchange surface first side which indirectlycontacts a liquid phase of the first heat exchange medium on the firstheat exchange surface second side disclosed herein, b) any percentage ofthe surface area of the first heat exchange surface second side whichcontacts the liquid phase of the first heat exchange medium disclosedherein, c) any volume ratio of the liquid phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) to the vapor phase of the first heatexchange medium in the first heat exchanger (or on the first heatexchange surface second side) disclosed herein, or d) any combinationthereof.

Statement 128. The reaction system of any one of Statements 124-127,wherein the heat exchange system further comprises i) a heat exchangemedium inlet line in fluid communication with one of the one or moreconduits of Statements 112-116, ii) a first control valve located on thefirst heat exchange fluid inlet line, iii) a heat exchange medium outletline in fluid communication with one of the one or more conduits ofStatements 112-116, and iv) a second control valve located on the heatexchange medium outlet line; wherein the first control valve isconfigured to control the addition of first heat exchange medium to theheat exchange system (or the first heat exchange medium circulation loopof Statement 116), and wherein the second control valve is configured tocontrol the removal of first heat exchange medium from the heat exchangesystem (or the first heat exchange medium circulation loop of Statement116).

Statement 129. The reaction system of Statement 128, wherein the firstlevel indicator and/or controller (coupled to the first heat exchanger)is configured to (a) actuate the first control valve to an open positionto add first heat exchange medium to the heat exchange system (or thefirst heat exchange medium circulation loop of Statement 116), and/or(b) actuate the second control valve to an open position to remove aportion of the first heat exchange medium from the heat exchange system(or the first heat exchange medium circulation loop of Statement 116).

Statement 130. The reaction system of any one of Statements 110-129,wherein the heat exchange system further comprises a second levelindicator and/or controller (coupled to the second heat exchanger and)configured to measure, monitor, and/or control the second level of theliquid phase of the first heat exchange medium on the second heatexchange surface first side.

Statement 131. The reaction system of Statement 130, wherein the secondlevel indicator and/or controller (coupled to the second heat exchangerand) is configured to control the second level of liquid phase of thefirst heat exchange medium of the second heat exchange surface firstside to be i) any percentage of the second heat exchange medium on thesecond heat exchange surface second side which indirectly contacts theliquid phase of the first heat exchange medium on the second heatexchange surface first side disclosed herein, ii) any volume ratio ofthe liquid phase of the first heat exchange medium in the second heatexchanger (or on the second heat exchange surface first side) to thevapor phase of the first heat exchange medium in the second heatexchanger (or on the second heat exchange surface first side) disclosedherein, or iii) any combination thereof.

Statement 132. The reaction system of any one of Statements 110-131,wherein the heat exchange system further comprise a liquid control valvelocated on at least one of the plurality of conduits of Statements113-116 allowing for flow of the first heat exchange medium from thesecond heat exchanger (or second heat exchange surface first side) tothe first heat exchanger (or the first heat exchange surface secondside).

Statement 133. The reaction system of Statement 132, wherein the liquidcontrol valve is configured to control a second level of the liquidphase of the first heat exchange medium in the second heat exchanger (oron the second heat exchange surface first side).

Statement 134. The reaction system of Statement 132 or 133, wherein theliquid control valve is configured to control a first level of theliquid phase of the first heat exchange medium on the first heatexchange surface second side.

Statement 135. The reaction system of any one of Statements 130-131,wherein the second level indicator and/or controller is configured toactuate the liquid control valve of Statements 130-132.

Statement 136. The reaction system of any one of Statements 110-135,wherein the reaction system further comprises a temperature indicatorand/or controller configured to measure, monitor, and/or control thereaction mixture temperature (or average reaction mixture temperature)within the reaction zone.

Statement 137. The reaction system of Statement 136, wherein thetemperature indicator and/or controller is coupled to the liquid controlvalve of any one of Statements 132-134.

Statement 138. The reaction system of Statement 136 or 137, whereintemperature indicator and/or controller is configured to actuate theliquid control valve of any one of Statements 132-137 to control thefirst level of the liquid phase of the first heat exchange medium in thefirst heat exchanger (or on the first heat exchange surface second side)and/or the second level of the liquid phase of the first heat exchangemedium in the second heat exchanger (or on the second heat exchangesurface first side) in response to the reaction mixture temperature (oraverage reaction mixture temperature).

Statement 139. The reaction system of any one of Statements 136-138,wherein the temperature indicator and/or controller is coupled to atleast one of the pressure control devices of any one of Statements117-124.

Statement 140. The reaction system of Statement 139, wherein thetemperature indicator and/or controller is configured to control apressure set point of at least one of the one or more pressure controldevices in response to reaction mixture temperature (or average reactionmixture temperature).

Statement 141. The reaction system of Statement 139 or 140, wherein thetemperature indicator and/or controller is coupled to the control valveof any one of Statements 122-124.

Statement 142. The reaction system of Statement 141, wherein thetemperature indicator and/or controller is configured to actuate thecontrol valve to control the pressure on the first heat exchange surfacesecond side and/or second heat exchange surface first side (and/or thefirst heat exchange medium) in response to the reaction mixturetemperature (or average reaction mixture temperature).

Statement 143. The reaction system of Statements 136-142, wherein thetemperature indicator and/or controller is a) coupled to at least one ofthe pressure control devices of any one of Statements 117-124 andconfigured to actuate the control valve of any one of Statements 122-124to control a pressure set point of the one or more pressure controldevices in response to reaction mixture temperature (or average reactionmixture temperature), b) coupled to the liquid control valve ofStatements 132-136 and configured actuate the liquid control valve to i)control a first level of the liquid phase of the first heat exchangemedium on the first heat exchange surface second side, ii) control thesecond level of the liquid phase of the first heat exchange medium onthe second heat exchange surface first side, or any combination thereof,c) is coupled with the first level indicator or controller of statement126 or 127 and configured to i) actuate the first control valve ofStatement 128 or 129 to allow the addition of first heat exchange mediumto the heat exchange system (or the first heat exchange mediumcirculation loop), and/or ii) actuate the second control valve ofStatement 128 or 129 to allow the removal of first heat exchange mediumfrom the heat exchange system (or the first heat exchange mediumcirculation loop) in response to reaction mixture temperature (oraverage reaction mixture temperature), or d) a combination thereof.

Statement 144. The reaction system of any one of Statements 110-143,wherein a second level of the liquid phase of the first heat exchangemedium on the second heat exchange surface first side is verticallyhigher relative to a common reference point on the ground than the firstlevel of the liquid phase of the first heat medium on the first heatexchange surface second side.

Statement 145. The reaction system of any one of Statements 110-144,wherein the second heat exchange surface comprises vertically orientedtubes or plates.

Statement 146. The reaction system any one of Statements 101-145,wherein the first heat exchange surface comprises horizontally orientedtubes or plates.

Statement 147. The reaction system of Statements 101-146, wherein thereaction system further comprises one or more reaction zone inlets tointroduce one or more reaction mixture components into the reaction zoneand one or more reaction zone outlets to remove reaction mixture fromthe reaction zone.

Statement 148. The reaction system of any one of Statements 101-147,where the first heat exchange medium has a boiling point at 1 atmosphere(101.3 kPa) greater than an average reaction mixture temperature on thefirst heat exchange surface first side and a boiling point at thepressure on the first heat exchange surface second side less than theaverage reaction mixture temperature on the first heat exchange surfacefirst side.

Statement 149. The reaction system of any one of Statements 101-148,wherein a ratio of heat exchanged reaction mixture volume to the totalreaction mixture volume within the reaction zone can have valuedisclosed herein (e.g., a minimum value of 1:1, 1.5:1, 2:1, 2.5:1, 3:1,or 4:1; a maximum value of 100:1, 50:1, 20:1, 15:1, 12:1, or 9:1; or ina range from 1:1 to 100:1, from 1.5:1 to 100:1, from 2:1 to 100:1, from3:1 to 100:1, from 4:1 to 100:1, from 3:1 to 50:1, from 3:1 to 20:1,from 4:1 to 50:1, from 4:1 to 15:1, or from 4:1 to 12:1; among othersdisclosed herein).

Statement 150. The reaction system of any one of Statements 101-149,where a temperature difference between an average reaction mixturetemperature on the first heat exchange surface first side and a firstheat exchange medium temperature on the first heat exchange surfacesecond side can be (or can be controlled to be) any temperaturedifference disclosed herein (e.g., less than 20° C., 15° C., 10° C. 7.5°C., 5° C., 4° C., or 3° C.).

Statement 151. The reaction system of any one of Statements 101-150,wherein the first heat exchange medium temperature on the first heatexchange surface second side can be (or can be controlled to be) withinany percentage of an average reaction mixture temperature on the firstheat exchange surface first side disclosed herein (e.g., 20%, 15%,12.5%, 10%, 7.5%, 6%, 5%, or 4.5%).

Statement 152. The reaction system of any one of Statements 101-151,wherein a reaction mixture temperature at any point in the reaction zonecan be, or can be controlled to be, within any value of an averagereaction mixture temperature in the reaction zone disclosed herein(e.g., within 15° C. 10° C., 7.5° C., 5° C., 4° C., 3° C., or 2° C.).

Statement 153. The reaction system of any one of Statements 101-152,wherein a reaction mixture temperature at any point in the reaction zonecan be, or can be controlled to be, within any percentage of an averagereaction mixture temperature in the reaction zone disclosed herein(e.g., within 3%, 2%, 1.5%, 1%, 0.8%, 0.6%, 0.5%, 0.45%, 0.4%, 0.35%,0.3%, 0.25%, or 0.2%).

Statement 154. The reaction system of Statements 101-153, wherein thereaction zone of the reaction system comprises at least a portion of thefirst heat exchange surface first side (of the first heat exchanger).

Statement 155. The reaction system of Statement 154, wherein thereaction system further comprises i) one or more reaction mixturecomponent feed lines configured to introduce one or more reactionmixture components into the first heat exchanger, and ii) reaction zoneoutlet lines which removes the reaction mixture from the reaction zoneor the first heat exchanger.

Statement 156. The reaction system of Statements 101-153, wherein thereaction zone of the reaction system comprises one or more reaction zonelines where i) at least one of the two or more reaction zone lines is areaction zone first heat exchanger inlet line(s) (containing thereaction mixture and) coupled to one or more first heat exchanger inletsconfigured to introduce the reaction mixture into the first heatexchanger to contact the reaction mixture with the first heat exchangesurface first side, ii) at least one of the two or more reaction zonelines is a reaction zone first heat exchanger outlet line(s) (containingreaction mixture and) coupled to one or more first heat exchangeroutlet(s) configured to remove reaction mixture from the first heatexchanger and from contacting the first heat exchange surface firstside.

Statement 157. The reaction system of Statement 156, wherein thereaction zone of the reaction system further comprises a motive devicefluidly connecting the reaction zone first heat exchanger inlet line(s)and the reaction zone first heat exchanger outlet line(s) configured toform a reaction mixture circulation loop, where the motive device isconfigured to circulate the reaction mixture through the reactionmixture circulation loop.

Statement 158. The reaction system of Statement 156 or 157, furthercomprising a reactor fluidly connected to a reaction zone first heatexchanger inlet line(s), a reaction zone first heat exchanger outletline(s), and first heat exchange surface first side.

Statement 159. The reaction system of any one of Statements 101-158,wherein the reaction system is selected from the group consisting of anethylene oligomerization reaction system, an ethylene trimerizationreaction system, an ethylene tetramerization reaction system, or anethylene trimerization and tetramerization reaction system.

Statement 159. The reaction system of Statements 156-159, w % herein thereaction system further comprises a) one or more reaction zone inlets(coupled to a reaction line), each reaction zone inlet configured tointroduce one or more of 1) ethylene, 2) a catalyst system or catalystsystem components comprising i) a heteroatomic ligand transition metalcompound complex and any organoaluminum compound, or ii) anyheteroatomic ligand, a transition metal compound, and an organoaluminumcompound, 3) optionally, a first organic reaction medium, and 4)optionally, hydrogen into a reaction mixture within the reaction zone,and b) one or more reaction zone outlets, each reaction outletconfigured to withdrawal reaction mixture from the reaction zone.

Statement 201. The process of Statement 46 or the reaction system ofStatement 160, wherein the heteroatomic ligand or the heteroatomicligand of the heteroatomic ligand transition metal compound complex hasstructure NPF 1, NPA 1, Gu 2, Gu 3, Gu 4, Gu 5, HCPA 1, or anycombination thereof;

wherein:R¹ is a hydrogen or a C₁ to C₂ organyl group;R² is a C₁ to C₂₀ organyl group;T is oxygen or sulfur;R^(2a) and R^(2b) independently are C₁ to C₂₀ organyl groups;L¹² and L²³ independently are C₂ to C₂₀ organylene groups;L²² is a C₃ to C₂₀ organylene groups;R³ is hydrogen or a C₁ to C₂₀ organyl group; andR⁴ and R⁵ independently are hydrogen or a C₁ to C₂₀ organyl groups;where R¹ and R² are optionally joined to form L^(12r), and L^(12r) is aC₃ to C₃₀ organylene group; andwhere R⁴ and R⁵ are optionally joined to form L⁴⁵, and L⁴⁵ is a C₄ toC₃₀ organylene group.

Statement 202. The process or reaction system of Statement 201, wherein:

R¹ is a hydrogen or a C₁ to C₂₀ hydrocarbyl group;

R² is a C₁ to C₂₀ hydrocarbyl group;

R^(2a) and R^(2b) independently are C₁ to C₂₀ hydrocarbyl groups;

L¹² and L²³ independently are C₂ to C₂₀ hydrocarbylene groups;

L²² is a C₃ to C₂₀ hydrocarbylene groups;

R³ is hydrogen or a C₁ to C₂₀ hydrocarbyl group; and

R⁴ and R⁵ independently are C₁ to C₂₀ hydrocarbyl groups;

where R¹ and R² are optionally joined to form L^(12r), and L^(12r) is aC₃ to C₂₀ hydrocarbylene group; and

where R⁴ and R⁵ are optionally joined to form L⁴⁵, and L⁴⁵ is a C₄ toC₂₀ hydrocarbylene group.

Statement 203. The process of Statement 46 or the reaction system ofStatement 155, wherein the heteroatomic ligand or the heteroatomicligand of the heteroatomic ligand transition metal compound complex hasstructure NRN 1, PRP 1, SRS 2, PNP 3, NRNRN 4, PRPRP 5, SRSRS 1, NRPRN1, or any combination thereof:

wherein:each R^(1s), R^(2s), R^(5s), R^(11s), R^(12s), R^(13s), and R^(14s),independently, is selected from a hydrogen or a C₁ to C₂₀ organyl group;each L^(1s), L^(3s), and L^(4s), independently, is selected from a C₂ toC₂₀ organylene group; andany two geminal R^(1s) are optionally joined to form L^(1sr), andL^(1sr) is a C₃ to C₃₀ organylene group;any two geminal R^(2s) are optionally joined to form L^(2sr), andL^(2sr) is a C₃ to C₃₀ organylene group;any germinal R^(11s) sand R^(12s) are optionally joined to formL^(12sr), and L^(12sr) is a C₃ to C₃₀ organylene group; andany germinal R^(13s) and R^(14s) are optionally joined to form L^(34sr),and L^(34sr) is a C₃ to C₃₀ organylene group.

Statement 204. The process or reaction system of Statement 203, wherein

each R^(1s), R^(2s), R^(5s), R^(11s), R^(12s), R^(13s), and R^(14s),independently, is selected from a hydrogen or a C₁ to C₂₀ hydrocarbylgroup;

each L^(1s), L^(3s), and L^(4s), independently, is selected from a C₂ toC₂₀ hydrocarbylene group;

any two geminal R^(1s) are optionally joined to form L^(1sr), andL^(1sr) is a C₂ to C₂₀ hydrocarbylene group;

any two geminal R^(2s) are optionally joined to form L^(2sr), andL^(2sr) is a C₂ to C₂₀ hydrocarbylene group;

any germinal R^(11s) and R^(12s) are optionally joined to form L^(12sr),and L^(12sr) is a C₂ to C₂₀ hydrocarbylene group; and

any germinal R^(13s) and R^(14s) are optionally joined to form L^(34sr),and L^(34sr) is a C₂ to C₂₀ hydrocarbylene group.

Statement 205. The process or reaction system of any one of Statements201-203, wherein the transition metal compound or the transition metalcompound of the heteroatomic ligand transition metal compound is achromium compound.

Statement 205. The process or reaction system of any one of Statements201-203, wherein the organoaluminum compound comprises an aluminoxane.While embodiments of the disclosure have been shown and described,modifications thereof can be made without departing from the spirit andteachings of the invention. The embodiments and examples describedherein are exemplary only, and are not intended to be limiting. Manyvariations and modifications of the invention disclosed herein arepossible and are within the scope of the invention.

What is claimed is:
 1. A process comprising: a) introducing at least 1)ethylene, 2) a catalyst system or catalyst system components comprisingi) a heteroatomic ligand transition metal compound complex and anorganoaluminum compound or ii) a heteroatomic ligand, a transition metalcompound, and an organoaluminum compound, 3) optionally, an organicreaction medium, and 4) optionally, hydrogen into a reaction mixturewithin a reaction zone; b) forming an oligomer product in the reactionzone; and c) controlling a reaction mixture temperature within thereaction zone with a heat exchange system comprising a first heatexchanger providing indirect contact between at least a portion of thereaction mixture and a first heat exchange medium, the first heatexchanger comprising a first heat exchange surface having i) a firstheat exchange surface first side in contact with the at least a portionof the reaction mixture, and ii) a first heat exchange surface secondside in contact with the first heat exchange medium: where a pressure onthe first heat exchange surface second side is less than 1 atmosphere(101.3 kPa), where the first heat exchange medium has a boiling point at1 atmosphere (101.3 kPa) greater than an average reaction mixturetemperature on the first heat exchange surface first side and a boilingpoint at the pressure on the first heat exchange surface second sideless than the average reaction mixture temperature on the first heatexchange surface first side, and where a temperature difference betweenthe average reaction mixture temperature on the first heat exchangesurface first side and a first heat exchange medium temperature on thefirst heat exchange surface second side is less than 20° C.
 2. Theprocess of claim 1, wherein a first part of the at least a portion ofthe reaction mixture on the first heat exchange surface first sideindirectly contacts a liquid phase of the first heat exchange medium onthe first heat exchange surface second side and a second part of the atleast a portion of the reaction mixture on the first heat exchangesurface first side indirectly contacts a vapor phase of the first heatexchange medium that are on the first heat exchange surface second side.3. The process of claim 2, wherein a volume ratio of the liquid phase tothe vapor phase of the first heat exchange medium on the first heatexchange surface second side is in a range from 1:1 to about 9:1.
 4. Theprocess of claim 2, further comprising: controlling the reaction mixturetemperature by controlling a first level of the liquid phase of thefirst heat exchange medium on the first heat exchange surface secondside, controlling the pressure on the pressure on the first heatexchange surface second side, or any combination thereof.
 5. The processof claim 4, wherein controlling the first level of the liquid phase ofthe first heat exchange medium comprises: adding or removing first heatexchange medium to or from the heat exchange system.
 6. The process ofclaim 4, wherein the first level of the liquid phase of the first heatexchange medium is controlled such that 50% to 90% of a surface area ofthe first heat exchange surface second side contacts the liquid phase offirst heat exchange medium.
 7. The process of claim 1, wherein the heatexchange system further comprises one or more pressure control devicesin fluid communication with the first heat exchange surface second side,the one or more pressure control devices providing the pressure of lessthan 1 atmosphere (101.3 kPa) on the first heat exchange surface secondside.
 8. The process of claim 7, further comprising: controlling apressure on the first heat exchange surface second side to provide thereaction mixture temperature within the reaction zone.
 9. The process ofclaim 8, wherein controlling a pressure on the first heat exchangesurface second side comprises adjusting a pressure set point on the oneor more pressure control devices.
 10. The process of claim 1, whereinthe heat exchange system further comprises a second heat exchangerproviding indirect contact between the first heat exchange medium and asecond heat exchange medium, the second heat exchanger comprising asecond heat exchange surface having i) a second heat exchange surfacefirst side in contact with the first heat exchange medium, and ii) asecond heat exchange surface second side in contact with the second heatexchange medium; where the second heat exchanger is fluidly connected tothe first heat exchanger via a plurality of conduits allowing for flowof the first heat exchange medium between the first heat exchangesurface second side and the second heat exchange surface first side,where the second heat exchange surface does not contact the reactionmixture, and where a pressure on the second heat exchange surface firstside is less than 1 atmosphere (101.3 kPa).
 11. The process of claim 10,wherein a first part of the at least a portion of the reaction mixtureon the first heat exchange surface first side indirectly contacts aliquid phase of the first heat exchange medium on the first heatexchange surface second side and a second part of the at least a portionof the reaction mixture on the first heat exchange surface first sideindirectly contacts a vapor phase of the first heat exchange medium onthe first heat exchange surface second side, and wherein at least afirst part of the second heat exchange medium on the second heatexchange surface second side indirectly contacts the vapor phase of thefirst heat exchange medium on the second heat exchange surface firstside and a second part of the second heat exchange medium on the secondheat exchange surface second side indirectly contacts liquid phase ofthe first heat exchange medium on the second heat exchange surface firstside.
 12. The process of claim 11, wherein controlling the reactionmixture temperature comprises: controlling a first level of the liquidphase of the first heat exchange medium on the first heat exchangesurface second side.
 13. The process of claim 12, wherein the firstlevel of the liquid phase of the first heat exchange medium on the firstheat exchange surface second side is controlled by: controlling a secondlevel of a liquid phase of the first heat exchange medium on the secondheat exchange surface first side, adding or removing first heat exchangemedium to or from the heat exchange system, or any combination thereof.14. The process of claim 10, wherein the heat exchange system furthercomprises one or more pressure control devices in fluid communicationwith at least one the one of the plurality of conduits, the one or morepressure control devices providing the pressure of less than 1atmosphere (101.3 kPa) on the first heat exchange surface second sideand on the second heat exchange surface first side.
 15. The process ofclaim 11, wherein a second level of the liquid phase of the first heatexchange medium on the second heat exchange surface first side isvertically higher relative to a common reference point on the groundthan the first level of the liquid phase of the first heat medium on thefirst heat exchange surface second side.
 16. The process of claim 10,wherein the first heat exchange surface comprises horizontally orientedtubes or plates, wherein the second heat exchange surface comprisesvertically oriented tubes or plates.
 17. The process of claim 1, whereinthe first heat exchange medium comprises water.
 18. The process of claim1, wherein a ratio of heat exchanged reaction mixture volume to thetotal reaction mixture volume within the reaction zone is in a rangefrom 0.7 to 1.0.
 19. The process of claim 1, wherein the first heatexchange medium temperature on the first heat exchange surface secondside is within 4.5% of the average reaction mixture temperature on thefirst heat exchange surface first side.
 20. The process of claim 1,wherein the reaction mixture temperature at any point in the reactionzone is within ±3% of the average reaction mixture temperature in thereaction zone.